WO2007049637A1

WO2007049637A1 - Composition for forming upper film and method for forming photoresist pattern

Info

Publication number: WO2007049637A1
Application number: PCT/JP2006/321247
Authority: WO
Inventors: Atsushi Nakamura; Hiroki Nakagawa; Hiromitsu Nakashima; Takayuki Tsuji; Hiroshi Dougauchi; Daita Kouno; Yukio Nishimura
Original assignee: Jsr Corporation
Priority date: 2005-10-27
Filing date: 2006-10-25
Publication date: 2007-05-03
Also published as: US8076053B2; US8435718B2; JP5578189B2; JP2012103738A; TW200731016A; KR20080056321A; JP5050855B2; EP1950610B1; US20100003615A1; JPWO2007049637A1; TWI418942B; KR101428121B1; US20120028198A1; KR20090091810A; EP1950610A4; EP1950610A1; KR100962951B1

Abstract

Disclosed is a composition for forming upper films which enables to form a coating film on a photoresist without causing intermixing with the photoresist film, which coating film is stable and does not dissolve into a medium such as water during immersion exposure, while being easily dissolved in an alkaline developing solution. Also disclosed is a method for forming a photoresist pattern. Specifically disclosed is a composition for forming an upper film, which covers a photoresist film for forming a pattern through irradiation of radiation. This composition is obtained by dissolving a resin, which is soluble in a developing solution for developing the photoresist film, in a solvent. The solvent has a viscosity at 20˚C of less than 5.2 × 10-3 Pa·s, and does not cause intermixing between the photoresist film and the composition for forming an upper film. In addition, the solvent contains an ether or a hydrocarbon.

Description

Specification

Upper layer film forming composition and photoresist pattern forming method

Technical field

[0001] The present invention forms a top layer film that protects a photoresist during immersion exposure used for lithography miniaturization and protects a lens of a projection exposure apparatus while suppressing elution of the photoresist component. The present invention relates to a useful composition for forming an upper layer film and a method for forming a photoresist pattern using the upper layer film.

Background art

[0002] When manufacturing a semiconductor element or the like, a stepper-type or step-and-scan method is used to transfer a reticle pattern as a photomask to each shot region on a photoresist-coated wafer via a projection optical system. A projection exposure apparatus of the type is used.

The resolution of the projection optical system provided in the projection exposure apparatus becomes higher as the exposure wavelength used is shorter and the numerical aperture of the projection optical system is larger. For this reason, with the miniaturization of integrated circuits, the exposure wavelength, which is the wavelength of radiation used in the projection exposure apparatus, has become shorter year by year, and the numerical aperture of the projection optical system has also increased.

Further, when performing exposure, the depth of focus is important as well as the resolution. The resolution and depth of focus δ are expressed by the following equations.

R = kl-λ / ΝΑ (i)

δ = k2- λ / ΝΑ ² (ii)

Where λ is the exposure wavelength, ΝΑ is the numerical aperture of the projection optical system, and kl and k2 are process coefficients. In order to obtain the same resolution R, it is short, and it is possible to obtain a large depth of focus δ by using radiation having a wavelength.

In this case, a photoresist film is formed on the exposed wafer surface, and the pattern is transferred to the photoresist film. In a conventional projection exposure apparatus, the space in which the wafer is placed is filled with air or nitrogen. At this time, when the space between the wafer and the lens of the projection exposure apparatus is filled with a medium having a refractive index _η , the resolution R and the depth of focus δ are expressed by the following equations.

δ = k2-n l / NA ² (iv)

For example, in the case of using water as the medium in the ArF process, when using a refractive index n = l.44 of light having a wavelength of 193 nm in water, the resolution R is smaller than that in exposure using air or nitrogen as a medium. 69. 4% (R = kl-(l / l. 44) ZNA), the focal depth is 144% (δ = k2-l. 44 λ / ΝΑ ² ).

The projection exposure method that can reduce the wavelength of the radiation for exposure and transfer a finer pattern is called immersion exposure, which is essential for miniaturization of lithography, especially in the order of several lOnm. It is considered a technology, and its projection exposure apparatus is also known (see Patent Document 1).

In the immersion exposure method using water as a medium for immersion exposure, the photoresist film formed on the wafer and the lens of the projection exposure apparatus are in contact with water. As a result, water may penetrate the photoresist film, reducing the resolution of the photoresist. In addition, the lens of the projection exposure apparatus may contaminate the lens surface due to the dissolution of the components constituting the photoresist into water.

[0004] Therefore, there is a method of forming an upper layer film on the photoresist film for the purpose of blocking the photoresist film from a medium such as water. However, this upper layer film is sufficiently transparent to the wavelength of radiation. A protective film can be formed on the photoresist film with little intermixing with the photoresist film, and a stable coating can be maintained without being eluted into a medium such as water during immersion exposure. It is necessary to form an upper layer film that can be easily dissolved in an alkaline solution or the like.

Patent Document 1: Japanese Patent Laid-Open No. 11-176727

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention has been made to cope with such problems, and has sufficient transparency at exposure wavelengths, particularly 248 nm (KrF) and 193 nm (ArF), and is almost intermixed with a photoresist film. A film can be formed on the photoresist without causing erosion, and a stable film can be maintained without leaching into a medium such as water during immersion exposure. It is an object of the present invention to provide an upper layer film-forming composition and a photoresist pattern forming method for forming an upper layer film that can secure the property and easily dissolve in an alkali developer.

Means for solving the problem

[0006] The present invention relates to an upper film-forming composition that is coated with a photoresist film for forming a pattern by irradiation with radiation, and the composition dissolves in a developer that develops the photoresist film. The fat is dissolved in a solvent, and the solvent has a viscosity of less than 5.2 × 10 ″ 3 Pa ′ s at 20 ° C. Further, the solvent contains a photoresist film and an upper film forming composition. The solvent is a solvent that does not cause intermixing.

Here, “no intermixing” refers to a case where it is determined that there is no intermixing between the resist coating and the upper film for immersion, according to the evaluation method of intermixing described later.

[0007] The solvent used in the upper layer film-forming composition of the present invention is characterized by containing a compound represented by the following formula (1).

[Chemical 3]

R ¹ — 0 — R ² (1) In formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 8 carbon atoms or a halogenated hydrocarbon group.

[0008] The other solvent contains a hydrocarbon compound having 7 to 11 carbon atoms.

The solvent containing the compound represented by the formula (1) or the hydrocarbon compound having 7 to 11 carbon atoms is a mixed solvent with a monohydric alcohol solvent having 1 to 10 carbon atoms.

[0009] The resin constituting the composition for forming an upper layer film of the present invention is a repeating unit having a group represented by the following formula (2), a repeating unit having a group represented by the following formula (3), It contains at least one repeating unit selected from the repeating unit having the group represented by (4), the repeating unit having a carboxyl group, and the repeating unit having a sulfo group, and measured by gel permeation mouth-matography method. The weight average molecular weight is 2,000-100,000.

R ⁵

(2 (3) In the formula (2), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms. In 3), R ⁵ represents a fluorinated alkyl group having 1 to 20 carbon atoms, and in formula (4), R ⁶ represents an organic group having a polar group.

The upper layer film-forming composition of the present invention is characterized in that CO 2 I and R contain at least one component selected from a _six acid component and an acid generator component that generates an acid upon irradiation. The method for forming a photoresist pattern of the present invention comprises a step of coating a photoresist on a substrate to form a photoresist film, and an upper film is formed on the photoresist film using the upper film forming composition of the present invention. And a step of forming a resist pattern by irradiating the photoresist film and the upper layer film with a liquid using a liquid as a medium through a mask having a predetermined pattern and then developing the process. .

The invention's effect

[0010] upper layer film forming composition of the present invention, the viscosity at 20 ° C of the solvent 5. is less than 2 X 10- ³ Pa 's, a reduction in the coating amount to uniformly applied to a silicon wafer The amount of application required can be reduced. In addition, since the solvent contains ethers represented by the formula (1) or a solvent having a hydrocarbon compound having 7 to 11 carbon atoms, the photoresist film is protected during immersion exposure used for lithography miniaturization. In addition, it is useful for forming an upper layer film that suppresses the dissolution of the photoresist component and protects the lens of the projection exposure apparatus. The upper layer film composition for immersion is mainly composed of monohydric alcohol as a solvent. Shows equivalent or better performance.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] When water is used as the immersion medium, the upper film obtained from the upper film-forming composition for immersion prevents direct contact between the photoresist film and water during immersion exposure, and allows water penetration. by It does not deteriorate the lithography performance of the photoresist film and prevents the lens of the projection exposure apparatus from being contaminated by components dissolved from the photoresist film.

As the solvent for dissolving the resin component of the upper layer film-forming composition, a solvent that hardly deteriorates the lithography performance by causing intermixing with the photoresist film when applied onto the photoresist film can be used.

It is preferable that the viscosity of the solvent in the present invention is 5. less than 2 X 10- ³ Pa 's. It is necessary to increase the coating amount for the viscosity of the solvent to ensure a certain the in-plane uniformity in 5. 2 X 10- ³ Pa 's or more. In the present invention, the viscosity of the solvent refers to the viscosity of the solvent as a whole.

The viscosity of the solvent 5. To less 2 X 10- ³ Pa 's, may include a solvent consisting of a solvent or a hydrocarbon having 7 to 11 carbon atoms containing an ether compound represented by the above formula (1) preferable. In the formula (1), R ¹ and R ² are each independently a hydrocarbon group having 1 to 8 carbon atoms or a halogenated hydrocarbon group.

Examples of the solvent containing ethers represented by the above formula (1) include jetyl ether, dipropinoreethenore, diisopropinoreethenore, butinoremethinoleethenore, butinoreethinoreether, butylpropyl ether, dibutyl ether , Diisobutyl ether, tert-butinoremethinoleatenore, tert-butinoleethinoleethenore, tert-butinorepropinoleether, di-tert-butyl ether, dipentyl ether, diisoamyl ether, dihexenoreatenore, Di-Cutinoreatenore, Cyclopentinoremethinoreetenore, Cyclohexinolemethinoreatenore, Cyclododecinoremethinoreatenore, Cyclopentinoreethinoreate Nore, Cyclohexinoreethinoreateoret , Cyclopentinole propinore Nore, cyclopentenole 2-propinoreethenore, cyclohexenorepropenoleethenore, cyclohexenole 2-propinoreethenore, cyclopentinolevinoleethenore, cyclopentinole tert-butinore etherenore, cyclohexenolev Chinoleatenore, cyclohexinole tert-butinoleethenore, bromomethinolemethinoleethenore, odomethylmethylether, _a , dichloromethinole methinoreatenore, chloromethinoleetinoreatenore, 2 —Chlorocetinoremethinoreethenore, 2-Bromocetinolemethinoleethenore, 2,2-Dichlorocetinolemethinoleethenore, 2-Chlorochinenoretinoreatenore, 2-Bromochinenoreetenore Ethinoleethenore, (±) — 1,2-Dichloroethyl 2-bromo-E Chino les ether Honoré, 2, 2, 2-triflate Honoré O Roe Chino milled by wet -Tenoré, Chloromethino Leoctinoreateore, Bromomethinoleoctinoleetenore, G-Chloetinoleetenore, Ethnorevininoreetenore, Butinorevininoreethenore, Arinoreetinore, Etenore, Arinorepropino Reethenore, Arinolevbutenoreethenore, Diaroleinetenore, 2-Methoxypropene, Ethyl-1-propenyl ether, 1-Methoxy-1,3 Butadiene, cis-l-Bromo-2-ethoxyethylene, 2-Chloro Ethyl vinyl ether, allyl 1, 1, 2, 2-tetrafluoroethyl ether, and preferred ethers include dipropyl ether, diisopropyl ether, butyl methyl ether, butinoreethenore, butinorepropinorete, and dibuty Noreete nore, diisobuty Noreatenore, t ert-Bucinore Mechinoleatere, tert-Butinore Ethinoreateoret, tert-Butinorepropinoreateore, G-tert-Butinoreatenore, Dipentinoreatenore, Diisoaminorete Nore Methinoleethenore, Cyclohexinolemethinoleetenore, Cyclopentinoleetinoleetenore, Cyclohexenoleetinoreatenore, Cyclopentinorepropinoreatenore, Cyclopentinore 2-Propinoleetenore, Cyclohexinorepropinoreatenore, cyclohexenole 2-propinoreatenore, cyclopentinolebutinoreatenore, cyclopentinole tert-butinoreethenore, cyclohexinorebutinoreethenore, cyclohexinore tert — Butyl ether .

[0013] In addition, as hydrocarbon solvents having 7 or more carbon atoms: L1, octane, isooctane, nonane, decane, methylcyclohexane, decalin, xylene, amylbenzene, ethylbenzene, diethylbenzene, tamen, and 2-butylbenzene , Cymen and dipentene.

[0014] The ethers and hydrocarbon solvents can be used alone or in combination with other solvents. Solvents that can be used in combination with the above ethers and hydrocarbon solvents include monohydric alcohols, polyhydric alcohols, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, aromatic carbonization. Examples include hydrogen, ketons, esters and water.

Monohydric alcohols include methanol, ethanol, 1 propanol, isopropanol, n-propanol, 2-methyl-1 propanol, n-butanol, 2-butanol, tert-butanol, 1 pentanol, 2 pentanol, 3 Pentanol, n-hexanol, cyclohexanol, 2-methyl-2-butanol, 3-methyl-2-butyl Tanol, 2-Methyl-1-butanol, 3-Methyl-1-butanol, 2-Methyl-1 pentanol, 2-Methyl-2 pentanol, 2-Methyl-3 pentanol, 3-Methyl 1 pentanol, 3-Methyl-2 pentanol, 3-methyl-3 pentanol, 4-methyl-1 pentanol, 4-methyl-2 pentanol, 2 ethyl 1-butanol, 2, 2 dimethyl-3 pentanol, 2, 3 dimethyl-3 pentanol, 2, 4 dimethyl-3 pentanol, 4, 4 Dimethyl-2-pentanol, 3-ethyl 3-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-2-hexanol, 2-methyl-3 hexanol, 5-methyl-1-hexanol , 5-Methylenole 2 hexanol, 2 ethynole 1 monohexanol, methylcyclohexa , Trimethylcyclohexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 1-octanol, 2-octanol, 3-octanol, 2 propylene 1 pentanol, 2, 4, 4 trimethyl-1-pentanol, 2, 6 Dimethyl-4 monoheptanol, 3 ethyl 2, 2 Dimethylpentanol, 1-nonanol, 2 Nonanol, 3, 5, 5 Trimethyl 1-hexanol, 1-decanol, 2 decanol, 4-decanol, 3, 7 Dimethyl-1-octanol, 3, 7 Dimethyl-3-octanol.

Among monohydric alcohols, monohydric alcohols with 4 to 8 carbon atoms are preferred 2 Methyl 1 propanol, 1-butanol, 2-butanol, 1 pentanol, 2-pentanol, 3 pentanol, 3-methyl- 2-Pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol and 2,4-dimethyl-3-pentanol are preferred. Polyhydric alcohols include ethylene glycol, propylene glycol, etc .; cyclic ethers such as tetrahydrofuran and dioxane; polyhydric alcohol alkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethylenol, ethylene Glycolic Resin Chilenoetinore, Ethylene Glyconore Monochino ether, Diethylene Glycolic Monomethinore ether, Diethylene Glyconore Monotino Ethenore, Diethylene Glycono Resin Metinore Ethenore, Diethylene Glycono Resin Chienore Diethylene glycol ether methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc .; alkyl of polyhydric alcohol Examples of ether acetates include ethylene glycol ether ether acetate, polyethylene glycol eno retinoate acetate, propylene glycol eno retinoate acetate, propylene glycol monomethyl ether acetate, and aromatic hydrocarbons. Benzene, toluene, xylene, etc .; ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, etc .; esters include ethyl acetate, butylacetate, 2-Hydroxypropionate, 2-Hydroxy-2-methylpropionate, 2-Hydroxy-2-methylpropionate, Ethoxyacetate, Hydroxyethylate, 2-hydride Kishi 3-methylbutanoate, methyl 3-methoxypropionate, 3-methoxy propionic acid Echiru, 3-ethoxy propionate Echiru, such as methyl 3-ethoxypropionate and the like.

Of these, monohydric alcohols, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, ketones, esters, and monohydric alcohols are preferred.

When the ethers or the hydrocarbon solvent having 7 to 11 carbon atoms is used in combination with another solvent, the ratio of the other solvent is preferably 75% by weight or less with respect to the whole solvent. By at 75 by weight% or less, 20 ° viscosity 5. 2 X 10- ³ Pa mixed solvent of C 'less than s, preferably ^{0. 7 X 10- 3 ~4. 0} X 10- 3 Pa' s. In addition, it is possible to reduce the required amount of the upper layer film-forming composition for uniform application on the silicon wafer, and to further suppress the elution of the key component from the composition.

The solvent that can be used in the present invention is a solvent that does not cause intermixing between the photoresist film and the upper layer film-forming composition.

For some solvents, such as tetrahydrofuran, propylene glycol monomethyl ether acetate, and methyl ethyl ketone, which may erode the resist film and cause intermixing, use the intermixing evaluation method described below. Therefore, it is preferable to use them together within a range where it is determined that there is no intermixing. In the case of the above solvents, it is 30% by weight or less, preferably 20% by weight or less, based on the whole solvent. If it exceeds 30% by weight, the photoresist film will be eroded and intermixed with the upper film. This causes problems such as the occurrence of defects and significantly degrades the resolution of the photoresist.

In the present invention, preferred examples of the solvent include ethers represented by the formula (1) wherein R ¹ and R ² are each independently a hydrocarbon group having 1 to 8 carbon atoms, and these ethers And a mixed solvent of a monohydric alcohol having 4 to 8 carbon atoms and a mixed solvent of a hydrocarbon compound having 7 to 11 carbon atoms and a monohydric alcohol having 4 to 8 carbon atoms.

[0018] The resin constituting the composition for forming an upper layer film of the present invention can form a stable film on a medium such as water upon irradiation with radiation, and is dissolved in a developer for forming a resist pattern. It is greaves.

Here, a film that is stable in a medium such as water at the time of radiation irradiation means that, for example, the change in film thickness is 3% or less of the initial film thickness as measured by the water stability evaluation method described later. .

Further, “dissolving in a developing solution after forming a resist pattern” means that the upper layer film is removed without any visual residue on the resist pattern after developing with an alkaline aqueous solution. That is, the resin according to the present invention is an alkali-soluble resin that hardly dissolves in a medium such as water and dissolves in the alkaline aqueous solution at the time of development using the alkaline aqueous solution after irradiation (hereinafter referred to as the present invention). The fat according to the invention is also called alkali-soluble fat

) o

Such an upper-layer film made of alkali-soluble resin prevents direct contact between the photoresist film and a medium such as water during immersion exposure, and may deteriorate the lithographic performance of the photoresist film due to the penetration of the medium. In addition, it prevents the lens of the projection exposure apparatus from being contaminated by components that elute from the photoresist film.

[0019] The coffin has a repeating unit having a group represented by the above formula (2), a repeating unit having a group represented by the above formula (3), and a group represented by the above formula (4). It includes at least one repeating unit selected from a repeating unit, a repeating unit having a carboxyl group, and a repeating unit having a sulfo group. These repeating units can be included in the resin by polymerizing a radically polymerizable monomer containing the unit and a polymerizable unsaturated bond.

[0020] In the repeating unit having a group represented by the formula (2), the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, and a butyl group. 1 to 4 fluorinated al The kill group is difluoromethyl group, perfluoromethyl group, 2,2-difluoroethyl group, 2,2,2 trifluoroethyl group, perfluoroethyl group, 2, 2, 3, 3-tetrafluoropropyl group. Perfluoroethyl group, perfluoropropyl group, 2, 2, 3, 3, 4, 4 xafluorobutyl group, perfluorobutyl group, 1,1 dimethyl-2, 2, 3 , 3-tetrafluoropropyl group and the like.

Of these, the perfluoromethyl group is preferred! /.

The repeating unit having a group represented by the formula (2) is a repeating unit having an alcoholic hydroxyl group containing at least one fluoroalkyl group on the carbon atom at the α-position in its side chain. Due to the electron-withdrawing property of the fluoromethyl group, the hydrogen atom of the alcoholic hydroxyl group is easily released and becomes acidic in an aqueous solution. Therefore, it becomes insoluble in pure water.

Preferable examples of the repeating unit having a group represented by the formula (2) include a repeating unit represented by the following formula (2a).

[Chemical 5]

(2a) In the formula (2a), R represents a hydrogen atom or a methyl group, R ⁷ represents an organic group, and preferably represents a divalent hydrocarbon group. Of the divalent hydrocarbon groups, a chain or cyclic hydrocarbon group is preferred.

Preferred R ⁷ is a methylene group, an ethylene group, a propylene group such as a 1,3 propylene group or a 1,2 propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an otatamethylene group, a nonamethylene group. , Decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecame group Tylene group, Hexadecamethylene group, Heptadecamethylene group, Octadecamethylene group, Nonadecamethylene group, Insalene group, 1-methyl 1,3 Propylene group, 2-Methyl 1,3-Propylene group, 2-Methyl 1 , 2 Propylene group, 1-methyl 1,4 butylene group, 2-methyl-1, 4-butylene group, methylidene group, ethylidene group, propylidene group, or 2 saturated chain hydrocarbon group such as propylidene group, 1, 3 cyclo Cyclobutylene groups such as butylene groups, cyclopentylene groups such as 1,3 cyclopentylene groups, cyclohexylene groups such as 1,4-cyclohexylene groups, cyclobutylene groups such as 1,5 cyclooctylene groups, etc. Carbon number 3 ~: Monocyclic hydrocarbon ring group such as cycloalkylene group of LO, norborene group such as 1, 4 norbornene group or 2, 5 norbornene group, 1, 5 Damanchiren group, 2, 6 Adamanchiren crosslinked cyclic hydrocarbon ring group, such as 2-4 hydrocarbon ring group of a cyclic carbon number 4 to 30, such as Adamanchiren group such group, and the like.

[0022] In particular, when R ⁷ contains a divalent aliphatic cyclic hydrocarbon group, carbon as a spacer between the bistrifluoromethyl-hydroxy-methyl group and the aliphatic cyclic hydrocarbon group. It is preferable to insert an alkylene group of the number 1 to 4! /.

In the formula (2a), R ⁷ is preferably a 2,5-norbornylene group, a hydrocarbon group containing a 2,6-norbornylene group, or a 1,2-propylene group.

[0023] In the repeating unit having a group represented by the formula (3), the fluorinated alkyl group having 1 to 20 carbon atoms of R ⁵ includes a difluoromethyl group, a perfluoromethyl group, 2, 2-difluoroethyl group, 2, 2, 2 trifluoroethyl group, norfluoroethyl group, 2, 2, 3, 3-tetrafluoropropyl group, perfluoroethyl group, perfluoropropyl group, 2, 2, 3, 3, 4, 4 Hexafluorobutyl group, perfluorobutyl group, 1, 1 dimethyl-2, 2, 3, 3, 3-tetrafluoropropyl group, 1, 1-dimethyl — 2, 2, 3, 3, 3 Pentafluoropropyl group, 2— (Nuorofluoropropyl) ethyl group, 2, 2, 3, 3, 4, 4, 5, 5—Otafluoropentyl group, perfur O-pentyl group, 1, 1 dimethyl-2, 2, 3, 3, 4, 4, 4-hexafluorobutyl group, 1, 1 dimethyl- 2, 2, 3, 3, 4, 4, 4-heptafluoro B Tyl group, 2- (N-fluorobutyl) ethyl group, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6-decafluoro-hexyl group, perfluoropentylmethyl group, perfluoro-hexyl group 1, 1-dimethyl 1, 2, 3, 3, 4, 4, 5, 5—octafluoropentyl, 1, 1— Dimethyl 2, 2, 3, 3, 4, 4, 5, 5, 5—Nonafluoropentyl group, 2— (Perfluoropentyl) ethyl group, 2, 2, 3, 3, 4, 4, 5, 5 , 6, 6, 7, 7—Dodecafluoro-heptyl group, perfluo-hexylmethyl group, perfluoro-heptyl group, 2- (perfluorohexyl) ethyl group, 2, 2, 3, 3, 4, 4, 5 , 5, 6, 6, 7, 7, 8, 8—tetradecafluorooctyl group, perfluorinated heptylmethyl group, perfluorooctyl group, 2- (perfluorinated heptyl) ethyl group, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9—hexadecafluoronol group, perfluorooctylmethyl group, perfluoronol group, 2-(Norflurooctyl) ethyl group, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10—octadecaful Olodecyl, perfluoronormethyl, perfluorodecyl, 2, 2, 3, 4, 4, 4— Xafluorobutyl group, 2, 2, 3, 3, 4, 4, 4-heptafluorobutyl group, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl Group, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8--tridodecafluorooctyl group, etc. Can do.

Among these, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorooctyl group are particularly preferable, but they are not limited to a nitrogen atom. This is because the acidity of the combined hydrogen becomes moderate.

Preferable examples of the repeating unit having a group represented by the formula (3) include a repeating unit represented by the following formula (3a).

[Chemical 6]

R

^: H ₂ — C-, \

c = o

/

^ (3a)

R ⁸

/

N H

I

o = s = o

R ⁵ In formula (3a), R represents a hydrogen atom or a methyl group, R ⁵ is Ru same der and R ⁵ of formula (3). R ⁸ represents an organic group, preferably a divalent hydrocarbon group. Of the divalent hydrocarbon groups, a chain or cyclic hydrocarbon group is preferred.

Preferred R ⁸ is a methylene group, an ethylene group, a propylene group such as a 1,3 propylene group or a 1,2 propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an otatamethylene group, a nonamethylene group. , Decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group, nonadecamethylene group, insalen group, 1-methyl 1,3 propylene group, 2-methyl 1,3-propylene group, 2-methyl 1,2 propylene group, 1-methyl 1,4 butylene group, 2-methyl-1,4-butylene group, methylidene group, ethylidene Group, propylidene group, or 2 saturated chain hydrocarbon group such as propylidene group, 1, 3 Cyclobutylene group such as cyclobutylene group, cyclopentylene group such as 1,3 cyclopentylene group, cyclohexylene group such as 1,4-cyclohexylene group, cyclobutylene group such as 1,5 cyclooctylene group, etc. Carbon number of 3 to: monocyclic hydrocarbon ring group such as cycloalkylene group of LO, norborene group such as 1,4 norborene group or 2,5 norbornene group, 1,5 adamantylene group, Examples thereof include bridged cyclic hydrocarbon ring groups such as hydrocarbon ring groups having 2 to 4 cyclic carbon atoms such as adamantylene groups such as 2, 6 adamantylene groups and the like.

[0025] In particular, when R ⁸ contains a divalent aliphatic cyclic hydrocarbon group, an alkylene group having 1 to 4 carbon atoms as a spacer between —NH group and the aliphatic cyclic hydrocarbon group Can be inserted.

R ⁸ is preferably a hydrocarbon group containing 2,5 norbornene group or 1,5 adamantylene group, ethylene group, 1,3 propylene group.

[0026] In the repeating unit having the group represented by the formula (4), R ⁶ represents an organic group having a polar group, preferably a hydrocarbon having a monovalent polar group having 1 to 20 carbon atoms. Group or a fluorinated hydrocarbon group.

Preferable examples of the repeating unit having a group represented by the formula (4) include a repeating unit represented by the following formula (4a).

[Chemical 7] R

\ (4a)

c = o

/

o

\

In the R ⁶ formula (4a), R represents a hydrogen atom or a methyl group, R ⁶ represents a residue of an alcohol having an ester bond with (meth) acrylic acid, and has a polar group.

Preferred examples of R ⁶ include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2 hydroxypropyl group, 3 hydroxypropyl group, 2 hydroxybutyl group, and 2, 3 dihydroxypropyl. Group, polypropylene glycol group, 2 hydroxycyclohexyl group, 4 hydroxycyclohexyl group, 3 hydroxy 1-adamantyl group, 3,5 dihydroxy 1-adamantyl group, aminomethyl group, 1 aminoethyl group, 2 aminoethyl group, 1-aminopropyl Group, 2 aminopropyl group, 3 —aminopropyl group, 2, 3 dihydroxypropyl group, 1, 2, 3 trihydroxypropyl group, difluoromethyl group, perfluoromethyl group, 2, 2-difluoroethyl group, 2, 2, 2 —Trifluoroethyl, perfluoroethyl, 1 ( -Fluoromethyl) ethyl group, 2 (perfluoromethyl) ethyl group, 2, 2, 3, 3-tetrafluoropropyl group, norfluoroethyl group, di (perfluoromethyl) methyl group Perfluoropropyl group, 1-methyl-2,2,3,3-tetrafluoropropyl group, 1 (perfluoroethyl) ethyl group, 2 (perfluoroethyl) ethyl group, 2, 2,3,3,4 Perfluoronol group, perfluorodecyl group, (2, 2, 2-trifluoroethyl) α carboxyl group, (perfluoroethylmethyl) dicarboxyl group, (2, 2, 2-trifluoroethyl) α-Carboki Cymethyl group, (2, 2, 2-trifluoroethyl) α-cyano group, (perfluoroethyl) α-cyano group, (2, 2, 3, 3, 3 pentafluoropropyl) 2 ethoxy group, (2, 2, 3, 3, 3 pentafluoropropyl) 2 cyano group. [0027] Examples of the radical polymerizable monomer that generates a repeating unit having a carboxyl group include (meth) acrylic acid, crotonic acid, cinnamic acid, atropic acid, 3-acetyloxy (meth) acrylic acid, 3-benzoyloxy ( Unsaturated monocarboxylic acids such as (meth) acrylic acid, α-methoxyacrylic acid, 3-cyclohexyl (meth) acrylic acid; unsaturated polycarboxylic acids such as fumaric acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid acids; unsaturated polycarboxylic acids mono-methylol Honoré Este Honoré, mono E Chino les Este Honoré, mono _eta - prop Honoré Este Honoré, monoesters such as monomethyl η- Buchinoree ester; 2- (meth) acrylamido 2 Methylpropanecarboxylic acid, 2-a carboxyacrylamide-2-methylpropanecarboxylic acid, 2a carboxymethyl Luamido 2-methylpropane carboxylic acid, 2 a-methoxycarbonyl acrylamide 2-methyl propane carboxylic acid, 2 a-acetyloxy acrylamide 2-methyl propane carboxylic acid, 2 a phenyl acrylamide 2-methyl propane Carboxylic acid, 2a monobenzylacrylamide 2-methylpropanecarboxylic acid, 2-a-methoxyacrylamide 2-methylpropanecarboxylic acid, 2a-cycloacrylamideacrylamide 2-methylpropanecarboxylic acid, 2a- Examples include cyanoacrylamide-2-methylpropanecarboxylic acid.

Of the above, (meth) acrylic acid and crotonic acid are preferred.

[0028] In addition, examples of the repeating unit having a carboxyl group include a radical polymerizable monomer represented by the formula (5).

[Chemical 8]

R

/

CH ₂ = C

\ (Five)

/

B

\

In the monomer represented by the COOH formula (5), R represents a hydrogen atom or a methyl group, A represents a single bond, a carbo group, a carbooxy group, an oxycarbo group, and B represents Single bond, divalent organic group having 1 to 20 carbon atoms. As a divalent organic group having 1 to 20 carbon atoms , Methylene group, ethylene group, propylene group such as 1,3 propylene group or 1,2 propylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, otatamethylene group, nonamethylene group, decamethylene group, undecamethylene group Group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptacamethylene group, octodecamethylene group, nonacamethylene group, insalen group, 1-methyl 1 , 3 Propylene group, 2-methyl 1,3 propylene group, 2-methyl 1,2 propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, methylidene group, ethylidene group, propylidene group Or a saturated chain hydrocarbon group such as 2-propylidene group, phenylene group, An arylene group such as a ylene group, a cyclobutylene group such as a 1,3 cyclobutylene group, a cyclopentylene group such as a 1,3 cyclopentylene group, a cyclohexylene group such as a 1,4 cyclohexylene group, 1, 5 A monocyclic hydrocarbon ring group such as a cycloalkylene group having 3 to 10 carbon atoms such as a cyclooctylene group such as a cyclooctylene group, or a norborn such as a 1,4 norbornylene group or a 2,5 norbolene group. -Bridged cyclic hydrocarbon ring groups such as 2- to 4-cyclic hydrocarbon ring groups such as adamantylene groups such as len, 1,5-adamantylene, 2,6-adamantylene, etc. .

The radically polymerizable monomer that generates a repeating unit having a sulfo group is represented by the formula (6).

[Chemical 9]

R

CH ₂ =

(6)

In the formula (6), A and B are the same as A and B in the formula (5). The formula (6) is obtained by replacing the carboxyl group in the formula (5) with a sulfo group.

Preferred monomers represented by the formula (6) include vinyl sulfonic acid, allyl sulfonic acid, 2 -(Meth) acrylamide-2-methyl-1-propanesulfonic acid, 4-bulu-1-benzenesulfonic acid. Of these sulfonic acid monomers, butyl sulfonic acid and aryl sulfonic acid are particularly preferred.

[0030] The resin component of the upper layer film-forming composition of the present invention includes the above-described repeating unit having a group represented by the formula (2), a repeating unit having a group represented by the formula (3), It includes at least one repeating unit having a repeating unit having a group represented by the formula (4), a repeating unit having a carboxyl group, and a repeating unit force having a sulfo group.

[0031] The resin component of the composition for forming an upper layer of the present invention may contain other radical polymerizable monomers for the purpose of controlling the molecular weight of the resin, the glass transition point, the solubility in a solvent, and the like. Can be copolymerized. “Other” means a radical polymerizable monomer other than the above-mentioned radical polymerizable monomers. Moreover, an acid dissociable group-containing monomer can be copolymerized.

Other radical polymerizable monomers or acid-dissociable group-containing monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec butyl (meth) acrylate. , Tert-butyl (meth) acrylate, isopropyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopenta- Luoxetyl (meth) acrylate, Isopolyol (meth) acrylate, Dicyclopental (meth) acrylate, Methoxydipropylene glycol (meth) acrylate, Butoxy monodipropylene glycol (meth) acrylate, Methoxy diethylene glycol (Meth) acrylate, methoxypropylene glycol (Meth) Talelate, 2-Methyl-2-adamantyl (meth) ate, 2-Ethyl-2-adamantyl (meth) ate, 2-Propyl-2-adamantyl (meth) ate, 2-butyl-2-adamantyl ( (Meth) Atalylate, 1-Methyl-1- 1-cyclohexyl (Meth) acrylate, 1-Ethyl 1-cyclohexyl (Meth) acrylate, 1-Propyl 1-cyclohexyl (Meth) ate, 1-butyl 1-cyclohexyl (meth) atarylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-propyl-1-cyclopentyl (meth) acrylate 1-butyl 1-cyclopentyl (meth) ate, 1-adamantyl 1-methylethyl (meth) ate, 1— Cyclo [2.2.1] heptyl - 1- Mechiruechiru (meth) Atari rate, etc. of (meth) § Crylic acid alkyl esters; Dicarboxylic acid diesters such as jetyl maleate, cetyl fumarate, and ethyl itaconate; (meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; Aromatic tols such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and -tolyl group-containing radical polymerizable monomers such as acrylonitrile and meta-titolyl-tolyl; Amide bond-containing radically polymerizable monomers such as acrylamide and methacrylamide; Fatty acid vinyls such as butyl acetate; Chlorine-containing radically polymerizable monomers such as salt and bullyidene; 1, 3 butadiene, Conjugated olefins such as isoprene and 1,4-dimethylbutadiene It is. Of these, (meth) acrylic acid alkyl esters, nitrile group-containing radical polymerizable monomers, amide bond-containing radical polymerizable monomers, and hydroxyl group-containing (meth) acrylic acid alkyl esters are preferred.

These monomers can be used alone or in combination of two or more.

[0032] When the above-mentioned other radical polymerizable monomer is copolymerized, the proportion thereof is preferably 50 mol% or less, more preferably 40 mol% or less, based on the whole polymer. V. If it exceeds 50 mol%, the solubility in an alkaline aqueous solution as a developing solution is lowered, and the upper layer film cannot be removed, and a residue may be generated on the resist pattern after development.

[0033] Examples of the polymerization solvent used in the production of alkali-soluble rosin include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene Alcohols such as glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Nolemonomethylol ether, diethylene glycol monoethyl ether, diethylene glycol monoresin methyl ether, diethylene glycol jetyl ether, diethylene glycol Chirumechirue Tenore, propylene glycol Honoré mono-methylol Honoré ether Honoré, alkyl ethers of polyhydric alcohols such as propylene glycol Honoré mono ethyl Honoré et one ether, ethylene glycol E chill ether acetate, diethylene E chill ether acetate, propylene glycol Alkyl ether acetates of polyhydric alcohols such as norethinoreethenoreacetate and propyleneglycololemonomethylenoreethenoreacetate; aromatic hydrocarbons such as toluene and xylene; acetone, methylethylketone, methylisobutylketone, Ketones such as cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, diacetone alcohol; ethyl acetate, butyl acetate, methyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropion Ethyl acid, Ethyl ethyl acetate, Ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, 3-Ethoxypro Examples include esters such as methyl pionate. Of these, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, ketones, and esters are preferred.

[0034] In addition, as a polymerization catalyst in radical copolymerization, a normal radical polymerization initiator can be used, for example, 2, 2'-azobisisobutyric-tolyl, 2, 2'-azobis mono (methyl 2-methylpropionate). ), 2, 2'-azobis (2,4 dimethylvaleronitrile), 2,2'-azobis (4 methoxy-2 dimethylvaleryl-tolyl), etc .; benzoyl peroxide, lauroyl belloxide Organic peroxides such as tert butyl peroxypivalate and 1,1 'bis (tert butyl peroxy) cyclohexane and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a redox initiator may be combined with a reducing agent.

[0035] The weight-average molecular weight (hereinafter abbreviated as Mw) of the alkali-soluble coconut resin obtained by the above method is usually from 2,000 to 100,000 in terms of polystyrene by gel permeation chromatography. 2,500 to 50,000, more preferred <3,000 to 20,000. In this case, if the Mw of the alkali-soluble resin is less than 2,000, the water resistance and mechanical properties as the upper layer film are remarkably low, while if it exceeds 100,000, the solubility in the aforementioned solvent is remarkably poor. Further, the ratio (MwZMn) of Mw of rosin and polystyrene-reduced number average molecular weight (hereinafter abbreviated as Mn) by gel permeation chromatography (GPC) is usually 1 to 5, preferably 1 to 3. is there.

It should be noted that the lower the impurities such as halogen, metal, etc. The coating property as a film and the uniform solubility in an alkali developer can be further improved. Examples of the purification method of coconut oil include chemical purification methods such as water washing and liquid-liquid extraction, and combinations of these chemical purification methods and physical purification methods such as ultrafiltration and centrifugation. Can do. In the present invention, rosin can be used alone or in admixture of two or more.

[0036] In the composition for forming an upper layer film for immersion according to the present invention, a surfactant may be blended for the purpose of improving coating properties, antifoaming properties, leveling properties and the like.

Examples of surfactants include BM-1000, BM-1100 (above, manufactured by BM Chemi Co., Ltd.), MegaFac F142D, F172, F173, F183 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Fluorad FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo SGM), Surflon S-112, S-113, S-131, S-141, Product names such as S-145 (above, Asahi Glass Co., Ltd.), SH-28PA, i-190, i-193, SZ-6032, SF-8428 (above Toray Dow Co., Ltd. Silicone Co., Ltd.) Commercially available fluorine-based surfactants can be used.

The amount of these surfactants is preferably 5 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin.

[0037] In addition, the composition for forming an upper layer film for immersion according to the present invention contains a low-sensitivity acid generator (hereinafter referred to as "acid generator"), acid, etc. for the purpose of improving the lithography performance of the resist. You can combine molecules.

Examples of the acid generator include (1) sulfonimide compound, (2) disulfonylmethane compound, (3) onium salt compound, (4) sulfone compound, (5) sulfonate compound, ( 6) Diazomethane compounds.

Examples of these acid generators are shown below.

(1) Sulfonimide compounds

As a sulfonimide compound, it represents with following formula (7), for example.

[Chemical 10]

In the above formula (7), R ^1Q represents a monovalent organic group, and R ⁹ represents a divalent organic group.

Monovalent organic groups include substituted or unsubstituted linear or branched alkyl groups, substituted or unsubstituted cyclic alkyl groups, substituted or unsubstituted aryl groups, perfluoroalkyl groups, etc. Divalent organic groups Examples thereof include a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted phenylene group. Specific examples of sulfonimide compounds include N (trifluoromethylsulfo-loxy) succinimide, N— (trifluoromethylsulfo-loxy) bicyclo [2.2.1] hepto-5-en-2,3 dicanoloxy Imido, N— (10—Camphorus Norehoninole

Xy) succinimide, N— (10-camphorsulfo-loxy) bicyclo [2.2.1] hept —5 hen 2,3 dicanolevoxyimide, N— (10-camphors norehoninole

7) oxabicyclo [2.2.1] hept-5-ene 2,3 dicanolepoxyimide, N— (p-toluenesulfo-loxy) succinimide, N— (p-toluenesulfo-loxy) bicyclo [2.2.1] hept-5-n 1,2,3 dicarboximide,

N- (4 trifluoromethylbenzenesulfo-loxy) succinimide, N- (4 trifluoromethylbenzenesulfo-loxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboximide, N- (Perfluorobenzenesulfo-loxy) sushi

N- (perfluorobenzenesulfo-oxy) bicyclo [2.2.1] hepto-5-ene 2,3 dicarboximide, N- (nonafluorobutylsulfonyloxy)

) Succinimide, N- (nonafluorobutylsulfo-loxy) bicyclo [2.2.1] hept —5 ene 2,3 dicarboximide, N— (perfluorooctanesulfooxyloxy) succinimide, N- (Perfluorooctanesulfo-luoxy) bicyclo [2.2.1] hepto-5-ene 2,3 dicarboximide, N- (benzenesulfol Oxy) succinimide, N— (benzenesulfo-loxy) bicyclo [2.2.1] hepto 5 —en-2,3 dicarboximide, N— (benzenesulfo-loxy) —7—oxabicyclo [2.2.1] hepto 5 1,3 Dicanoloxyimide, N— {(5-Methyl w5c ■ l-Carboxymethanebicyclo [2. 2. 1] hepter 2-yl) sulfo-luo

R

Examples include succinimide vcll and the like.

(2) Disulfo-Lumethane oos = = Compound

The disulfonylmethane compound is represented by the following formula (8), for example.

[Chemical 11]

R ¹²

In the formula, R ¹¹ and R ¹² are each independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or other monovalent other group having a hetero atom. V and W each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group or another monovalent organic group having a hetero atom. And at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or V and W and each other form a group represented by the following formula (8-1)!

[Chemical 12]

V ′ and W ′ are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or the same or different carbon atoms. V 'and W' bonded to atoms are connected to each other to form a carbon monocycle A plurality of V ′ and w ′ may be the same or different from each other. R is an integer of 2 to 10.

(3) Onium salt compounds

Examples of the salt salt compounds include ododonium salt, sulfo-um salt, phospho-um salt, diazo-um salt, ammonium salt, pyridinium salt and the like.

Specific examples of the salt compound include bis (4 t-butylphenol) odoyuumnona fluorobutane sulfonate, bis (4 t-butylphenol) odo-umtrifluorethane sulfonate, bis (4 t Butylphenol) iodine perfluorooctane sulfone, bis (4 t-butylphenol) iodine p-toluenesulfonate, bis (4 t-butylphenol) iodide-um 10 camphorsulfonate, 4 trifluoromethyl Tylbenzenesulfonate, bis (4 t-butylphenol) odoperum Fluorobenzene Benzene sulfonate, diphenol-nonafluorobutane sulfonate, diphenol-umtrifluoromethane sulfonate, diphenol Umperfluo mouth octane nore honate Reensnorephonate, Diphenylo-um benzene sulphonate, Dipheo-Rhodenum 10—Camphors sulphonate, Di-Fuel rhododonium 4 Trifluoromethylbenzene sulfonate, Diphloe-Lord-Umperfluo Robenzene sulfonate, triphenyl sulfone nonafluoro Robutane sulfonate, triphenyl sulfone-mutrifluoromethane sulfonate, triphenyl-norethnorejo-perfunoreo-reooctanesnorephonate, trie-noresnorephonium p 10-camphorsulfonate, triphenylsulfo-um 4 trifluoromethyl benzenesulphonate, triphenyl-noresnorephone Mu Perfluoronole benzene sulphonate, 4-hydroxyphenol 'diphenylsulfo-mu-trifluoromethanesulfonate, tri (p-methoxyphenol) sulfo-munonafluorobutanesulfonate, tri (ρ-methoxyphenol) -L) sulfo-mu-trifluoromethanesulfonate, tri (p-methoxyphenol) sulfo-perfluorooctanesulfonate, tri (p-methoxyphenol) sulfo-um p-toluenesulfonate, tri ( p-methoxyphenol) sulfo-benzenebenzene sulfonate, tri- (p-methoxyphenol) sulfo-sulfur 10-camphorsulfonate, bis (p-fluoro) Mouth-Fuel) Jodonium trifluoromethanesulfonate, bis (p-fluorophenol) mono-nonafluoromethanesulfonate, bis (p-fluorophenol) jordoncanphan sulfonate, (p-fluorophenol) ) (Fuel) odo-um trifluoromethane sulfonate, Tris (p fluorophenol) sulfo-mu trifluoromethane sulfonate, Tris (p fluorophenyl) sulfo-um p Toluene sulfonate , (P Fluorophthalate) Diphenylsulfo-mu-trifluoromethanesulfonate, 1- (4-n-butoxynaphthyl) tetrahydrothiophene-nonafluoro-n-butanesulfonate, triphenylsulfo-um 1, 1, 2, 2-tetrafluoro-2- (tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dodecane 8-yl) Ethanesulfonate, trifluorosulfone, 1, 1-difluoro 2— (tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dodecane 1-8-yl) ethane sulfonate, 1 (4 — Η-Butoxynaphthyl) tetrahydrothiophene 1, 1, 2, 2—tetrafluoro 1- (tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dodecane 1— Le) ethanesulfonate, 1 - (4-.eta. butoxynaphthyl) tetrahydropyran Chio Hue - ©-time 1, 1-difluoro-2-(Te Torashikuro ^{[4. 4. 0. I 2 '.} 5 l 7' 10] dodecane 1-yl) ethane sulfonate

[0041] (4) Sulfone compound

Examples of the sulfone compound include 13-ketosulfone, 13 sulfonylsulfone, diazo compounds thereof, and the like.

Specific examples of the sulfone compound include phenacylphenolsulfone, mesitylphenolsulfone, bis (phenolsulfol) methane, 4-trisphenacylsulfone, and the like.

[0042] (5) Sulfonic acid ester compound

Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, and the like.

Specific examples of sulfonic acid ester compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzene 9, 10 Toxanthracene 2-sulfonate, α-methylol benzoin tosylate, α-methylol benzoin η-octane sulfonate, α-methylol benzoin trifluoromethane sulfonate, a-methylol benzoin n-dodecane sulfonate, etc. Can be mentioned.

[0043] (6) Diazomethane Compound

Examples of the diazomethane compound include a compound represented by the following formula (9).

[Chemical 13]

In the formula, R ¹³ and R ¹⁴ each independently represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

Specific examples of diazomethane compounds include bis (trifluoromethanesulfol) diazomethane, bis (cyclohexanesulfol) diazomethane, bis (benzenesulfol) diazomethane, bis (ptoluenesulfol) diazomethane, Methanesulfol p Toluenesulfonyldiazomethane, cyclohexanesulfodiluene 1, 1 Dimethylethylsulfonyldiazomethane, bis (1,1 dimethylethanesulfol) diazomethane, bis (3,3 dimethyl 1 , 5 Dioxaspiro [5.5] dodecane 1-sulfol) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7 sulfo-diazomethane), bis (t-butylsulfonyl) diazomethane, and the like.

[0044] Among the above acid generators, the acid generators are preferred.

Bis (4 t-butylphenol) odo-umtrifluoromethanesulfonate, bis (4-tert-butylphenol) odo-um perfluoro-n-butanesulfonate, bis (4 tert-butylphenol) podonium p— Toluene sulfonate, bis (4 t-butylphenol) iodine 10-camphor sulfonate, bis (4-tert-butylphenol) iodine 2 trifluoromethylbenzenesulfonate, bis (4 t-butylphenol) iodine 4 trifluor Romethylbenzenesulfonate, bis (4 t-butylphenol) Um 2, 4 difluorobenzenesulfonate, triphenylsulfo-trifluoromethane sulfonated sulfonate, triphenylenosordoneperf peroleoloneo n-butanesulfonate, trifluorosulfone sulfonate p —Toluenesulfonate, triphenylsulfo-sulfuric acid 10—Strong earth sulfonate, triphenol-nolesnorephonium 2—Triphenololeromethinolebenzenesulphonate, triphenylsulfo-sulfur 4 Trifluoro Methylbenzenesulfonate, trifluorosulfone 2,4 difluoromethylbenzenesulfonate, N— (trifluoromethanesulfo-loxy) succinimide, N- (trifluoromethanesulfo-loxy) bicyclo [2.2.1 ] Heptone 1,5 2,3 Dicarboximide, N— (10-camphorsulfo-loxy) succin Mido, N— (10-camphorsulfo-loxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboximide and N— {(5-methyl-5-carboxymethanebicyclo [2. 2. 1] Hepter 2-yl) sulfoloxy} succinimide, bis (4 t-butylphenol) jordon perfluorooctane sulfonate, diphenyl odomonnonafluorobutane sulfonate, diphenol -Rhodonium Fluorometas Norehonate, Diphne Noreno Perfu Noreo Octanes Norehonate, Diphne Noredo -Um 10-Camphors Norehonate, Triféno Nore Nore Honorum Perfluoro-octane sulfonate, tri (p-methoxyphenol) sulfo-trifluoromethanesulfonate, tri (ρ-methoxyphenol) sulfone 10-camphor sulfonate, bis (p fluorophenol) iodine trifluoromethane sulfonate, bis (p fluorophenol) iodine nonafluoromethane sulfonate, bis (p fluorophenol) iodine Mucamphor sulfonate, (p-fluorophenyl) (phenol) odo-umtrifluoromethanesulfonate, tris (pfluorophenyl) sulfo-mutrifluoromethanesulfonate, tris (p-fluorophenyl) sulfo- Um p-toluenesulfonate, (p-fluorophenyl) diphenylsulfo-mu-trifluoromethanesulfonate, N— {(5-methyl-5 carboxymethanebicyclo [2.2.1] hepter 2 yl) sulfo- Roxy} succinimide, N— (nonafluorobutylsulfo-luoxy) bicyclo [2.2.1] -5-1,2-dicarboximide, N- (p-toluenesulfo-loxy) succinimide, N- (benzenesulfo-loxy) bicyclo [2.2.1] hept-5-en 2,3 dicarboximide , Bis (cyclohexanesulfol) diazomethane, bis (3,3-dimethyl) -1, 5 Dioxaspiro [5.5] dodecane 1-sulfo) diazomethane, bis (1,4-dioxaspiro [4.5] decane 7-sulfo-) diazomethane, bis (t-butylsulfol) Diazomethane, 1- (4-n-butoxynaphthyl) tetrahydrothiophene-nonauroro- _n -butanesulfonate, triphenylsulfo-um 1, 1, 2, 2-tetrafluoro 1- (tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] Dodecane 1-yl) ethane sulfonate, triphenyl sulfone · 1,1-difluoro-2 (tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ^'10] dodecane 8 I le) ethanesulfonate, 1 one (4-.eta. butoxynaphthyl) Tetorahidorochi old Fueniumu-1, 1, 2, 2-tetrafluoro-2-(tetracyclo [4. 4. 0. I ^{^{^{^{2 '5. I 7' 10}}}} ] dodecane one 8 I le) ethanesulfonate, 1 (4-.eta. butoxynaphthyl) Tetorahidorochi Ofue - ©-time 1, 1-difluoro-2-group (tetracyclo ^{[.. 4. 4. 0. I 2} '5 1 7] dodecane one 8 I le) ethanesulfonate It is preferable to use at least one selected from force. Examples of the acid include carboxylic acids and sulfonic acids.

Examples of these carboxylic acids and sulfonic acids are shown below.

Examples of low molecules such as carboxylic acids and sulfonic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, 2-methylpropanoic acid, 2-ethylbutanoic acid, 2 methylbutanoic acid, 3 methylbutanoic acid, 2,2 dimethylbutanoic acid, tert butylacetic acid, ( Sat) 2-Methylpentanoic acid, 2-Propylpentanoic acid, 3-Methylpentanoic acid, 4-Methylpentanoic acid, 2-Methylhexanoic acid, (±) -2-Ethylhexanoic acid, 2-Methylheptanoic acid, 4 —Methyloctanoic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, succinic acid Succinic acid, methylbutanedioic acid, 2,2-dimethylbutanedioic acid, 2-ethyl-2-methylbutanedioic acid, 2,3 dimethylbutanedioic acid, glutaric acid, 2-methyldaltaric acid, 3-methyldaltaric acid, 2,3 dimethyldal Taric acid, 2,4-dimethyldaltaric acid, 3,3-dimethyldaltaric acid, adipic acid, 3-methyladipic acid, 2,2,5,5-tetramethyladipic acid, pimelic acid, suberic acid, azelain Acid, Cenosinic acid, 1,11-Undecanedi Norebonic acid, Undecanedioic acid, 1,12-Dodecanediol Rubonic acid, Hexadecanedioic acid, 1, 2, 3 Propanetricarboxylic acid, 2-Methyl-1, 2, 3 Propanetricarboxylic acid, 1, 2, 3, 4 Butanetetracarboxylic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoic acid, heptafluorobutanoic acid, hexafluoroglutaric acid, glycolic acid, 2-hydroxyisobutanoic acid 2-hydroxy-2-methylbutanoic acid, 2-ethyl-2-hydroxybutanoic acid, (±) -2 hydroxy-1-3-methylbutanoic acid, (±) -2 hydroxy-1-4-methylpentanoic acid, (±) -2 hydroxy Oxanoic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, D-marinic acid, (R)-(-)-citramaric acid, (shi) 2-isopropylmarinic acid, 3-hydroxy 1 3-methyldaltaric acid, D tartaric acid, L-tartaric acid, citric acid, (1R, 3R, 4R, 5R) — (—)-kini Acid, methoxyacetic acid, ethoxyacetic acid, 3-methoxypropionic acid, (1) -menthoxyacetic acid, (1) -tetrahydro-2 furonic acid, (1) 1 tetrahydro-1 furonic acid, thiolacetic acid, thiopivalic acid, 2 mercaptopropionic acid, 3 —Mercaptopropionic acid, mercaptobutanedioic acid, (methylthio) acetic acid, thiodiglycolic acid, 3,3′-dithiodipropionic acid, 3-carboxylpyrudisulfide, (±) -2- (carboxymethylthio) butane Diacid, 2, 2 ', 2 ", 2"' — [1, 2 ethanediylidenetetrakis (thio)] tetrakisacetic acid, (±) -3-methyl-2-oxopentanoic acid, 5-oxohexanoic acid, 6- Oxoheptanoic acid, 4, 6-dioxoheptanoic acid, 2 oxopentanedioic acid, 2-oxohexanoic acid, 4 oxoheptanedioic acid, 5-oxononanni Cis-Pinonic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentylacetic acid, 3-cyclopentylpropionic acid, cyclohexylacetic acid, dicyclohexylacetic acid, cyclohexanepropionic acid, cyclohexanebutanoic acid, cyclohexanepentanoic acid, 1-methyl 1-cyclohexanecarboxylic acid, (±) -2-methyl- 1-cyclohexanecarboxylic acid, (shi) -3-methyl-1-cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 4 tert-butylcyclo Hexanecarboxylic acid, trans-4 pentylcyclohexanecarboxylic acid, 4-methylcyclohexane acetic acid, (R) (-)-hexahydromandelic acid, (S) (+) -hexahydromandelic acid, 3-methoxy Cyclohexanecarboxylic acid, 4-methoxycyclohexanecarboxylic acid, cycl Heptanoic acid, 2 norbornane acetic acid, [1R- (2 endo, 3 exo)] - 3 hydrate port carboxymethyl one 4, 7, 7-trimethyl bicyclo [2.2.1] heptane one 2 acetate, (+) - camphor 1 rubonic acid, (1) 1 camphor carboxylic acid, cis bicyclo [3. 3. 0] octane 1 2-carboxylic acid, 1-oxotricyclo [2. 2. 1. 0 ² ' ⁶ ] heptane 1 7- Carboxylic acid, 3-Noradamantane power norlevonic acid, 1-adamantane-powered norevonic acid, 1-adamantaneacetic acid, 3-methyl 1-adamantaneacetic acid, trans-DL-1,2, 2-cyclopentanedicarboxylic acid, 1,1-cyclopentanediacetic acid, (IS , 3R) — (—) — camphoric acid, 1, 1-cyclohexane diacetic acid, (shi) trans-1, 2, 2-cyclohexane dicarboxylic acid, (soil) 1 1,3 cyclohexane dicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid, 1,3 adamantandicanolevonic acid, 1,3,5 cyclohexanetriforce norevonic acid, (1 α, 3 α, 5 α)-1, 3, 5 trimethyl-1, 3, 5 cyclohexanetricarboxylic acid, (1 α, 3 α, 5 β)-1, 3, 5 Trimethyl-1, 3, 5 Cyclohexanetricarboxylic acid, 1, 2, 3, 4 Cyclobutanetetracarboxylic acid, cis, cis, cis, cis-1, 2, 3, 4 -Cyclopentanetetracarboxylic acid, 1, 2, 3, 4, 5, 6 Cyclohexanehexacarboxylic acid, benzoic acid, phenol acetic acid, 1-phenol 1-cyclopentanecarboxylic acid, α-cyclohexane Xylphenylacetic acid, diphenylacetic acid, triphenylacetic acid, 2-furylpropionic acid, 3-furolpropionic acid, 2 benzil 3,3 dimethylbutanoic acid, 2,2 diphenylpropionic acid, 3, 3, diphenylpropionic acid, 3, 3, 3 triphenylpropionic acid, 2 phenolbutanoic acid, 2 ethyl-2-phenolbutanoic acid, 3 phenolbutanoic acid, 4 phenolbutanoic acid, 5 phenol -Lupentanoic acid, 3-Methyl-2 Phenolpentanoic acid, 6-Phenolhexanoic acid, α-Fluoro-Fulacerate Acid, (R) () 1 α-methoxyphenylacetic acid, phenoxyacetic acid, 3 phenoxypropionic acid, (±) -2 phenoxypropionic acid, 11-phenoxyundecanoic acid, 2-phenoxybutanoic acid, ) Monomandelic acid, (±) α-methyoxyacetic acid, 2-hydroxy-3-phenolpropionic acid, tropic acid, thiophenoxyacetic acid, S-benzylthioglycolic acid, 2-ethylthio-2,2-diphenol Acetic acid, benzoylformic acid, phenylvirbic acid, 3-benzoylpropionic acid, 4-benzoylbutanoic acid, ferromalonic acid, benzylmalonic acid, ferrobutanedioic acid, 3-phenolpentanedioic acid, ο tolyl Acetic acid, 1,2-phenol-diacetic acid, (±) -1-benzocyclobutene canrebonic acid, 1, 2, 3, 4 tetrahydro-2-naphthoic acid, (α, α, α-Trifanole o ο Tolyl) acetic acid, 2-fluorophenylacetic acid, 2-chlorophenol acetic acid, 2-bromine Mofe-acetic acid, (±) -2- (2-chlorophenoxy) propionic acid, 2-methoxyphenol acetic acid, (±) 2-methoxymandelic acid, 3- (2-methoxyphenyl) propionic acid, 1 ,

2-phenol-dioxydiacetic acid, 2-hydroxyphenylacetic acid, 2--trophenylacetic acid,

3— (2-Trophenyl) —2-oxopropanoic acid, 2 Formylphenoxyacetic acid, Homophthalic acid, m-Tolylacetic acid, (a, a, α-Trifluoro-m-tolyl) acetic acid, 3-Hydroxyphene -Luoacetic acid, 3-methoxyphenylacetic acid, 3-methoxymandelic acid, 3--trifluoroacetic acid, ρ-tolylacetic acid, (4 methylphenoxy) acetic acid, 3-fluorophenylacetic acid, 4-isobutyl-a-methylphenolacetic acid, 4— (4-Dichlorodi) tributoxy) butanoic acid, 1,4 phenol-diacetic acid, 4 fluorophenolacetic acid, (α, α, α-trifluoro-ρtolyl) acetic acid, 4 (trifluoromethyl) ) Mandelic acid, 3— (4 Fluorobenzoyl) Propionic acid, 4 Chronophenol acetic acid, 4 Bromophenol acetic acid, 3, 3, 3-Tris (4 — Chroophthalol) propionic acid, 4 — (Bromomethyl) phenolacetic acid, 1 (4 Chlorophenyl) 1-Cyclopentanecarboxylic acid, 3- (4 Chlorobenzone) propionic acid, 1 (4-methoxyphenyl) cyclopentanecarboxylic acid, 1 (4-methoxyphenyl) cyclohexane Carboxylic acid, 4-methoxyphenylacetic acid, 4-ethoxyphenylacetic acid, 3- (4-methoxyphenyl) propionic acid, 4- (4-methoxyphenyl) butanoic acid, 4-hydroxyphenylacetic acid, 2- (4-hydroxy (Phenoxy) propionic acid, 3- (4-hydroxyphenol) propionic acid, (M) 4-methoxymandelic acid, 4-chlorophenoxyacetic acid, Bis (4-chlorophenoxy) acetic acid, 4, 4-Bis (4-hydroxyphenol) pentanoic acid, 4-bromomandelic acid, 4 (dimethylamino) furacetic acid, 4-trophylacetic acid, 2- (4-trifluorophenyl) propionic acid, 4 (4 -Trov -L) butanoic acid, 3- (4-methoxybenzoyl) propionic acid, 4-hydroxyphenol biruvic acid, D-3-phenolic acid, 4 fluorophenoxyacetic acid, (±) -2— ( 4-chlorophenoxy) propionic acid, 2- (4-chlorophenoxy) 2-methylpropionic acid, 9, 10 dihydro-1,2-phenanthrenebutanoic acid, 9,10 dihydro-1, γ-year-old xanthone 2, phenanthrenebutanoic acid (2,4-di-tert-pentylphenoxy) acetic acid, 2,6 difluorophenol acetic acid, 2,4 difluorophenol acetic acid, 2,5 difluorophenylacetic acid, 3,4 difluorophenol acetic acid, 3,5-difluorophenylacetic acid, 4-chloro-tri-loxyacetic acid, 3,5-bis (tri Fluoromethyl) phenolacetic acid, (3,4-dimethoxyphenol) acetic acid, 3,4- (methylenedioxy) phenolacetic acid, 3 fluoro-4-hydroxyphenylacetic acid, 5-methoxy-1-acetanone-3 —Acetic acid, 3— (3,4-dimethoxyphenol) propionic acid, 4 -— (3,4-dimethoxyphenol) butanoic acid, (2,5 dimethoxyphenol) acetic acid, (4 hydroxy mono 3— (Methoxyphenyl) acetic acid, (±) -4-hydroxy-1-3-methoxymandelic acid, (±) -3-hydroxydioxy-4-methoxymandelic acid, DL—3,4 dihydroxymandelic acid, 2,5-dihydride Loxyphenylacetic acid, 3,4-dihydroxyphenolacetic acid, 3,4-dihydroxyhydrocinic acid, 4-hydroxy-1-trifluoroacetic acid, podocapic acid, 2,5 dihydroxy-1,4 benzenediacetic acid, 3, 4, 5 Trimethoxyphenol Acid, 3— (3, 4, 5 trimethoxyphenol) propionic acid, 2, 3, 4, 5, 6 pentafluorophenylacetic acid, 4-biphenylacetic acid, 1 naphthylacetic acid, 2 naphthylacetic acid, ( ±) α-trityl-2-naphthalenepropionic acid, (1 naphthoxy) acetic acid, (2 naphthoxy) acetic acid, (+) -6-methoxy-α-methyl-2-naphthalene acetic acid, 9 fluorene acetic acid, 2 methylbenzoic acid, 2-fluorobenzoic acid, 2-Trifluoromethylbenzoic acid, 2-methoxybenzoic acid, 2-ethoxybenzoic acid, salicylic acid, thiosalicylic acid, 2--trobenzoic acid, 2-(ρ-toluoyl) benzoic acid, 3-methylbenzoic acid, 3 -Fluorobenzoic acid, 3-Trifluoromethylbenzoic acid, 3-Methoxybenzoic acid, 3-Hydroxybenzoic acid, 3-Dimethylaminobenzoic acid, 3-Nitrobenzoic acid, 4-Methylbenzoic acid, 4 Ethyl benzoic acid, 4-propyl benzoic acid, 4 isopropyl benzoic acid, 4 butyl benzoic acid, 4 tert butyl benzoic acid, 4 pentyl benzoic acid, 4 monohexyl benzoic acid, 4 1 heptyl benzoic acid, 4-octyl benzoic acid, 4 Fluorobenzoic acid, 4 Trifluoromethylbenzoic acid, 4, 4'- (Hexafluoroisopropylidene) bis (benzoic acid), 4, 4'-oxybis (benzoic acid), 4-methoxybenzoic acid , 4- (trifluoromethoxy) benzoic acid, 4-ethoxybenzoic acid, 4 propoxybenzoic acid, 4 pentyloxybenzoic acid, 4 monohexyl

Loxybenzoic acid, 4-heptyloxybenzoic acid, 4-octyloxybenzoic acid, 4-noroxybenzoic acid, 4-decyloxybenzoic acid, 4-undecyloxybenzoic acid, 4-dodeoxyoxybenzoic acid, 4-isopropoxybenzoic acid, 4-hydroxybenzoic acid Acid, 4 (Methylthio) benzoic acid, 4 (Ethylthio) benzoic acid, 4-Dimethylaminobenzoic acid, 4 (G (Tyramino) benzoic acid, 4-12 trobenzoic acid, 4-acetyl benzoic acid, 4 carboxybenzaldehyde, phthalic acid, isophthalic acid, 1, 2, 3 benzenetricarboxylic acid, terephthalic acid, 1, 2, 4 benzenetricarboxylic acid, 1 , 3, 5 Benzenetricarboxylic acid, 1, 2, 4, 5 Benzenetetracarboxylic acid, benzenehexacarboxylic acid, 2, 3 Dimethylbenzoic acid, 2,6 Dimethylbenzoic acid, 3 Fluoro-2-methylbenzoic acid, 2, 3 Difluorobenzoic acid, 2, 6 Difluorobenzoic acid, 2 Fluoro-6 trifluoromethylbenzoic acid, 2 Fluoro-3 trifluoromethylbenzoic acid, 2, 6 bis (trifluoromethyl) benzoic acid, 2, 3 dimethoxy Benzoic acid, 2, 6 Dimethoxybenzoic acid, 3-Methylsalicylic acid, 3-Isopropylsalicylic acid, 3-Methoxysalicylic acid, 3-Hydroxysa Cyric acid, 6-hydroxysalicylic acid, 2-methyl-6-trobenzoic acid, 3-methyl-2--trobenzoic acid, 2-methyl-3-trobenzoic acid, 3-methoxy-2-trobenzoic acid, 3-trophthalic acid, 2,4 Dimethylbenzoic acid, 2,5 Dimethylbenzoic acid, 5 Fluoro-2-methylbenzoic acid, 3 Fluoro-4 methylbenzoic acid, 2,4 Bis (trifluoromethyl) benzoic acid, 2,5 Bis (trifluoromethyl) benzoic acid Acid, 2, 4 difluorobenzoic acid, 3, 4 difluorobenzoic acid, 2 fluoro-4 trifluoromethylbenzoic acid, 2, 5 difluorobenzoic acid, 3-methoxy-4-methylbenzoic acid, 3 fluoro-4 methoxybenzoic acid, 2 , 4 Dimethoxybenzoic acid, 2,5 dimethoxybenzoic acid, 3,4 dimethoxybenzoic acid, 3,4-diethoxybenzoic acid, piperoluccinic acid, 3-hydroxy-4-methyl Benzoic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 5-fluorosalicylic acid, 2-methoxy-4 (methylthio) benzoic acid, 5-methoxysalicylic acid, 4-methoxysalicylic acid, 4-hydroxy-3-methoxybenzoic acid, 3-hydroxy-4 -Methoxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,5 dihydroxybenzoic acid, 2,4 dihydroxybenzoic acid, 4-jetylaminosalicylic acid, 5-methyl-2-torobenzoic acid, 4-methyl-3-torobenzoic acid 3-methyl-4-trobenzoic acid, 2-methyl-5--torobenzoic acid, 2-fluoro-5-torobenzoic acid, 4-fluoro-3-to-benzoic acid ゝ 4-methoxy-1-3-nitrobenzoic acid, 3-methoxy-one 4-Nitrobenzoic acid, 3-Hydroxy —4-Trobenzoic acid, 2 Hydroxy-5-trobenzoic acid, 2, 4 Dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 4-methylphthalic acid, 4-hydroxyisophthalic acid, 4-to Lophthalic acid, nitroterephthalic acid, 1,4 phenylene dipropionic acid, 3,5 dimethylbenzoic acid, 3,5-di-tert-butylbenzoic acid, 3,5-difluorobenzoic acid, 3,5-bis ( Trifluoromethyl) benzoic acid, 3,5-dimethoxybenzoic acid, 3,5-dihydroxybenzoic acid, 3,5-dinitrobenzoic acid, 5-tert-butylisophthalic acid, 5--troisophthalic acid, 5 — (4-Carboxy-2-trophenoxy) isophthalic acid, 2, 3, 4 trifluoro oral benzoic acid, 2, 3, 6 trifluorobenzoic acid, 2, 4, 6 trimethylbenzoic acid, 2, 4, 6 — trifluorobenzoic acid 3, 4, 5-trifluorobenzoic acid, 3, 4, 5-trimethoxybenzoic acid, 3, 4, 5 triethoxybenzoic acid, 2 hydroxy-3 isopropyl-6 methylbenzoic acid, 2 hydroxy-6 isopropyl-3 methylbenzoic acid 3, 5 Diisopro Pyrsalicylic acid, 3,5 di-tert-butyl-4-hydroxybenzoic acid, 2,3,4 trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 3-hydroxy-4,5-dimethoxybenzoic acid, 4-hydroxy —3,5 Dimethoxybenzoic acid, 4,5 Dimethoxy-2-to oral benzoic acid, 4-methyl-3,5-dinitrobenzoic acid, 4-hydroxy-3,5-dinitrobenzoic acid, 3,5 dinitrosalicylic acid, 3-hydroxy-4-methyl- 2-Trobenzoic acid, 2, 3, 4 Trimethoxybenzoic acid, 2, 4, 5 Trifluorobenzoic acid, 2, 4, 5 Trimethoxybenzoic acid, 2, 5 Dihydroxyterephthalic acid, 2, 3, 4, 5—Tetrafluoro Benzoic acid, 2, 3, 5, 6-terafluorobenzoic acid, 2, 3, 5, 6-terafluoro 4-methylbenzoic acid, pentafluorobenzoic acid, tetrafluoroterephthalic acid, tetrafluoroloy Phthalic acid, tetrafluorophthalic acid, 2-biphenylcarboxylic acid, 4'-hydroxy-4 biphenylcarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2 benzylbenzoic acid, 2 -bibenzylcarboxylic acid, 2, 3, 4, 5, 6 Pentafluorophenoxyacetic acid, 2 phenoxybenzoic acid, 3 phenoxybenzoic acid, 4 phenoxybenzoic acid, 2 benzoylbenzoic acid, 3 benzoylbenzoic acid, 4 benzoylbenzoic acid, 2— ( 4 Fluorobenzoyl) benzoic acid, 4 [4 2 carboxybenzoyl) phenol] butanoic acid, 1 naphthalene carboxylic acid, 2 naphthalene carboxylic acid, 4 fluoro-1-naphthalene carboxylic acid, 1-hydroxy 2-naphthalene carboxylic acid, 2-hydroxy 1 naphthalene carboxylic acid, 3 hydroxy 2 naphthalene carboxylic acid, 2 ethoxy 1 naphthalene carboxylic acid, 1, 4 dihydride Roxy-2-naphthalenecarboxylic acid, 3,5-dihydroxy-2-naphtho Talen carboxylic acid, 1, 4 naphthalene dicarboxylic acid, 2, 3 naphthalene dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid, 1- (8 carboxy) naphthaldehydride, 2 biphenol-lencanolevonic acid, 9-funole renolenic acid nolevonic acid, 1-furole Nylon acid, 4-Hunolenic acid, 9 Hydroxy 1-fluorene carboxylic acid, 9 Hydroxy 9 Fluorene carboxylic acid, 9 Fluorene 1-carboxylic acid, 9 Fluorene mono 2-carboxylic acid, 9 Fluorene-4 1-strength rubonic acid, 7—-tro 9 9xo 4 fluorene carboxylic acid, 9 anthracene carboxylic acid, 9, 10 anthracene dipropionic acid, xanthene —9-carboxylic acid, 2, 7 di-tert-butyl 9, 9 dimethyl 4 , 5 Xanthene dicarboxylic acid, 2, 2 '-(ethylenedioxy) dialin N, N, Ν', N 'tetraacetic acid, Carbogenyloxy 1-Methylalanine, Ν— (4—-Trobenzoyl) — β-Alanine, ァ acetylyl 2 Fluoro DL Phenylalanine, Ν Acetyl 3— Funoleo DL DL Phenonoalanine, Ν Acetenore 4 Funeo Leo DL Phenylenolananine, methanesulfonic acid, ethanesulfonic acid, taurine, 3— [(1, 1-dimethyl 1-2 hydroxyxetyl) amino] — 2 hydroxy— 1-propanesulfonic acid, 3— [bis (2 hydroxyformicyl) amino ] — 2-Hydroxy— 1-propanesulfonic acid, (1R)-(-)-10 —Camphorsulfonic acid, (1S) — (+) — 10-Camphorsulfonic acid, trifluoromethylsulfonic acid, perfluorobutanesulfone Acid, perfluorooctane sulfonic acid, (methylamino) sulfonic acid, (butylamino) sulfonic acid, 1, 1, 2, 2— Tiger fluoro-2-(tetracyclo ^{[4. 4. 0. I 2 '.} 5 l 7' 10] dodecane one 8-I le) ethanesulfonic acid, 1, 1 - difluoro-2-(tetracyclo [4. 4. 0. I ² ^'5. 1 "°] dodecane one 8-I le) ethanesulfonic phosphate and the like.

Of the above carboxylic acids and sulfonic acids, preferred / acids are exemplified below.

Acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearin Acid, 2-methylpropanoic acid, 2-ethylbutanoic acid, 2 methylbutanoic acid, 3 methylbutanoic acid, 2,2 dimethylbutanoic acid, tert-butylacetic acid, (±) 2-methylpentanoic acid, 2 propylpentanoic acid, 3 Methyl pentanoic acid, 4-methylpentanoic acid, 2-methylhexanoic acid, (shi) 2-ethylhexa Acid, 2-methylheptanoic acid, 4-methyloctanoic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, succinic acid, methylbutanedioic acid, 2,2 dimethylbutanedioic acid , 2-ethyl-2-methylbutanedioic acid, 2,3 dimethylbutanedioic acid, glutaric acid, 2-methyldaltaric acid, 3-methyldaltaric acid, 2,3 dimethyldaltaric acid, 2,4 dimethyldaltaric acid, 3,3 dimethyldaltal Acid, adipic acid, 3 methyl adipic acid, 2, 2, 5, 5-tetramethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1, 11-undecanedicarboxylic acid, undecanedioic acid, 1 , 12 dodecanedicarboxylic acid, hexadecanedioic acid, 1, 2, 3 propanetricarboxylic acid, 2-methyl-1,2,3 prononetricarboxylic acid, 1, 2, 3, 4 butante Lacarboxylic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoic acid, heptafluorobutanoic acid, hexafluoroglutaric acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, citric acid (1) Menthoxyacetic acid, thioacetic acid, thiobivalic acid, (methylthio) acetic acid, thiodiglycolic acid, (2) 2- (carboxymethylthio) butanedioic acid, 2, 2 ', 2 ", 2"'-[1,2-Ethandidiylidenetetrakis (thio)] tetrakisacetic acid, (±) -3-methyl-2-oxopentanoic acid, 5-oxohexanoic acid, 6-oxoheptanoic acid, 2-oxopentanedioic acid, 2-oxo Hexanedioic acid, 4-oxoheptanedioic acid, 5-oxononannic acid, cyclopentanecarboxylic acid, cyclopentylacetic acid, 3-cyclopentyl Lopionic acid, cyclohexylacetic acid, dicyclohexylacetic acid, cyclohexanepropionic acid, cyclohexanebutanoic acid, cyclohexanepentanoic acid, (±) -2-methyl 1-cyclohexanecarboxylic acid, (±) — 3-methyl 1-cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 4-tert-butylcyclohexanecarboxylic acid, trans-4 pentylcyclohexanecarboxylic acid, 4-methylcyclohexaneacetic acid, 3-methoxycyclohexane Xanthcarboxylic acid, 4-methoxycyclohexane carboxylic acid, cycloheptanecarboxylic acid, 2-norbornane acetic acid, [lR— (2-endo, 3 — exo)] — 3 Hydroxy 1, 4, 7, 7 Trimethylbicyclo [2.2.1] ] Heptane-2-acetic acid, (+)-camphorcarboxylic acid, (1-) monocamphorcarboxylic acid, cis bicyclo [3.3.0] octane-2 Carboxylic acids, anti-one 3- Okisotorishikuro [2.2.2 1.0 ^{^2'6]} heptane one 7-carboxylic acid, 3 Nora Dammann Tan carboxylic acid, 1-§ Damman Tan carboxylic acid, 1-§ Damantane acetic acid, 3-methyl 1-adamantane acetic acid, trans- DL—1, 2 cyclopentane dicarboxylic acid, 1, 1-cyclopentane diacetic acid, (IS, 3R) — (—) — camphoric acid, trans— 1,2 cyclohexanedicarboxylic acid, (±) -1,3 cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3 adamantanedicarboxylic acid, 1,3,5 cyclo Hexanetricarboxylic acid, (1 α, 3 α, 5 α)-1, 3, 5 Trimethyl— 1, 3, 5 Cyclohexanetricarboxylic acid, (1 α, 3 α, 5 j8)-l, 3, 5 Trimethyl- 1, 3, 5 cyclohexanetricarboxylic acid, cis, cis, cis, cis-l, 2, 3, 4-cyclopentanetetracarboxylic acid, 1, 2, 3, 4, 5, 6 Xanthhexacarboxylic acid, benzoic acid, phenacetic acid, 2-phenolpropionic acid, 3-phenolpropionic acid, α-fluorofe- Acetic acid, 3 Phenoxypropionic acid, (±) -2 Phenoxypropionic acid, (±) α-Methoxyphenylacetic acid, ο Tolylacetic acid, 1, 2-Furenediacetic acid, 1, 2, 3 , 4 Tetrahydro-2 naphthoic acid, (α, α, α trifanololeol ο tolyl) acetic acid, 2-fluorophenol acetic acid, 2-methoxyphenol acetic acid, 2 — trifluoroacetic acid, 3 — (2 — — Trophyl) —2-oxopropanoic acid, (a, a, α-trifluoro-m-tolyl) acetic acid, 3--trifluoroacetic acid, 3-fluorophenylacetic acid, 4-fluorophenylacetic acid, (a, a, α-trifluoro-p-tolyl) acetic acid, 4-trophenylacetic acid, 4 fluorophenoxyacetic acid, 2,6 difluorophenol acetic acid, 2,4 difluorophenol acetic acid, 2,5 difluorophenol acetic acid, 3, 4 Difluorophenol acetic acid, 3, 5 Difluorophenol acetic acid, 3 , 5-bis (trifluoromethyl) phenolacetic acid, 3-fluoro-4-hydroxyhydroxyacetic acid, (2,5-dimethoxyphenyl) acetic acid, 4-hydroxy-3-to-phenylacetic acid, 2 , 3, 4, 5, 6 Pentafluorophenylacetic acid, 1 naphthylacetic acid, 2 naphthylacetic acid, (1 naphthoxy) acetic acid, (2-naphthoxy) acetic acid, 2-fluorobenzoic acid, 2 trifluoromethylbenzoic acid 2-fluorobenzoic acid, 3-fluorobenzoic acid, 3-trifluoromethylbenzoic acid, 3-methoxybenzoic acid, 4-fluorobenzoic acid, 4-trifluoromethylbenzoic acid, 4-trobenzoic acid, 3-fluoro-2-methylbenzoic acid 2,3 difluorobenzoic acid, 2,6 difluorobenzoic acid, 2 fluoro-6 trifluoromethylbenzoic acid, 2 fluoro-3 trifluoromethylbenzoic acid, 2, 6 bis (trifluoromethyl) benzoic acid Acid, 2-Methyl-6-trobenzoic acid, 3-Methyl-2-to Oral benzoic acid, 2-methyl-3-trobenzoic acid, 5 fluoro-2-methylbenzoic acid, 3 fluoro-4-methylbenzoic acid, 2,4 bis (trifluoromethyl) benzoic acid, 2,5 bis (trifluoromethyl) Benzoic acid, 2,4 difluorobenzoic acid, 3,4 difluoro oral benzoic acid, 2 fluoro-4 trifluoromethylbenzoic acid, 2,5 difluorobenzoic acid, 3 fluoro-4-methoxybenzoic acid, 5-methyl-2-trobenzoic acid Acids, 4-methyl 3-utrobenzoic acid, 3-methyl-4-torobenzoic acid, 2-methyl-5-torobenzoic acid, 2-fluoro-5-torobenzoic acid, 4-fluoro-3-torobenzoic acid, 4-methoxy 3—-Torobenzoic acid, 3—Methoxy-1 4-—Torobenzoic acid, 3-Hydroxy-1-4-Torobenzoic acid, 2 Hydroxy-5-Torobenzoic acid, 2,4 Dinitrobenzoic acid, 3,4-Dinitrobenzoic acid Acid, 3,5-difluorobenzoic acid, 3,5-bis (trifluoromethyl) benzoic acid, 3,5 dinitrobenzoic acid, 2, 3,4 trifluorobenzoic acid, 2, 3, 6- trifluorobenzoic acid, 2, 4, 6 Trifluorobenzoic acid, 3, 4, 5 Trifluorobenzoic acid, 4-methyl-3, 5-dinitrobenzoic acid, 4-hydroxy-3, 5-dinitrobenzoic acid, 3, 5 Di-trosalicylic acid, 2, 4, 5 Trifluorobenzoic acid, 2, 3, 4, 5-tetrafluorobenzoic acid, 2, 3, 5, 6-tetrafluorobenzoic acid, 2, 3, 5, 6-tetrafluoro4 methylbenzoic acid, pentafluorobenzoic acid, 2, 3 , 4, 5, 6 Pentafluorophenoxyacetic acid, 1 Naphthalenecarboxylic acid, 2 Naphthalenecarboxylic acid, 4 Fluoro-

1-Naphthalenecarboxylic acid, 1-Hydroxy-1-2-Naphthalenecarboxylic acid, 2-Hydroxy-1 Naphthalenecarboxylic acid, 3 Hydroxy2 Naphthalenecarboxylic acid, 1,4-Dihydroxy2 Naphthalenecarboxylic acid, 3,5 Dihydroxy-2 Naphthalenecarboxylic acid , 1, 4 Naphthalenedicarboxylic acid, 2, 3 Naphthalenedicarboxylic acid, 2, 6 Naphthalene dicanolevonic acid, Methanesolephonic acid, Ethansenorephonic acid, Taurine, 3— [(1, 1-Dimethinole — 2 hydroxyethyl) amino] 2 Hydroxy 1 Propanesulfonic acid, 3-[bis (

2-Hydroxyethyl) amino]-2-hydroxy— 1-propanesulfonic acid, (1R) — (—) — 10-camphors norphonic acid, (1S)-(+) —10—camphors norphonic acid, trifnoleo L-methylsulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, (methylamino) sulfonic acid, (butylamino) sulfonic acid, 1, 1, 2, 2—tetrafluoro 1- (tetracyclo [4 4. 0. I ² ' ^5. L ⁷ ' ¹⁰ ] Dodecane 8-yl) ethanesulfonic acid, 1, 1-difluoromethyl-2-(tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] dodecane one 8-I le) is preferable to use at least one selected the group power of Etansu sulfonic acid.

[0047] The acid generator and the acid can be used alone or in admixture of two or more.

The compounding amount of the acid generator and the acid is 10 parts by weight or less, preferably 0.0015 parts by weight, more preferably 0.0053 parts by weight with respect to 100 parts by weight of the resin. In this case, if the blending amount of the acid generator and the acid exceeds 10 parts by weight, the lens of the projection exposure apparatus tends to be contaminated by components eluted from the upper layer film-forming composition.

[0048] Furthermore, an acid diffusion controller may be blended with the upper film forming composition for immersion according to the present invention for the purpose of improving the lithography performance of the resist.

Examples of the acid diffusion controller include a compound represented by the following formula (10) (hereinafter referred to as “nitrogen-containing compound (1)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (1)”). , “Nitrogen-containing compound (Π)”), diamino polymer having 3 or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compound, urea compound, And nitrogen-containing heterocyclic compounds.

[Chemical 14]

R ¹⁵

R1S― _N I ― _R 15 (10)

In the formula, R ¹⁵ may be the same or different from each other, and may be a hydrogen atom, an alkyl group, an aryl group or a aralkyl group. Including the case where it is substituted with a group.

[0049] Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-xylamine, n-ptylamine, n-octylamine, n-norlamin, and n-decylamine; di-n-butylamine, di-n-pentylamine , Di-n-xyllamines, di-n-peptylamines, di-n-octylamines, di-n-no-lamines, di-n-decylamines and other dialkylamines; , Trialkylamines such as tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-no-lamine, tri-n-decylamine; aline, N-methylamine -Aromatic amines such as -phosphorus, Ν, Ν dimethylamine, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-12 troanilin, diphenylamine, triphenylamine, 1-naphthylamine and the like.

[0050] Examples of the nitrogen-containing compound (Π) include ethylenediamine, Ν, Ν, Ν ', Ν' tetramethylethylenediamine,,, Ν ', Ν'-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylene Diamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphene-lamine, 2,2 'bis (4 aminophenol) propane, 2- (3-aminophenol) 2- (4-aminophenol) propane, 2- (4-aminophenol) 2 (3-hydroxyphenol) propane, 2- (4 aminophenol) 2— (4 hydroxyphenol) propane, 1,4—bis [1 (4-aminophenol) 1 1-methylethyl] benzene, 1,3 bis [1 (4-aminophenol) E) 1-methylethyl] benzene etc. .

Examples of the nitrogen-containing compound (ΠΙ) include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, and the like.

[0051] Examples of the amide group-containing compound include formamide, Ν-methylformamide, Ν, ホル -dimethylformamide, acetoamide, アミド -methylacetamide, Ν, ジメチル dimethylacetamide, propionamide, benzamide, pyrrolidone, Ν- And methyl pyrrolidone. Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3 dimethylurea, 1,1,3,3-tetramethylurea, 1,3 diphenyl-urea, and tributylthiourea. .

Nitrogen-containing heterocyclic compounds include, for example, imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2 phenolimidazole, 2-phenol penzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Ν-methyl 4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, atalidine, etc. Of pyridines, pyrazine, pyrazole, pyridazine, quino Examples include zalin, purine, pyrrolidine, piperidine, monoreforin, 4-methinoremonorephorin, piperazine, 1,4-dimethylbiperazine, 1,4 diazabicyclo [2.2.2] octane.

[0052] As the acid diffusion controller, a base precursor having an acid dissociable group can also be used. Specifically, N— (t-butoxycarbol) piperidine, N— (t-butoxycarbol) imidazole, N— (t-butoxycarbol) benzimidazole, N— (t— (Butoxycarbonyl) 2-phenolpenimidazole, N— (t-butoxycarbonyl) dioctylamine, N— (t-butoxycarbol) diethanolamine, N— (t-butoxycarbonyl) dicyclohexylamine, N— (t-butoxycarbol) diphenylamine and the like.

Of these nitrogen-containing organic compounds, nitrogen-containing compounds (I) and nitrogen-containing heterocyclic compounds are preferred. Of the nitrogen-containing compounds (I), trialkylamines are particularly preferred. Among the nitrogen-containing heterocyclic compounds, imidazoles are particularly preferred.

The acid diffusion controller can be used alone or in admixture of two or more.

[0054] The compounding amount of the acid diffusion controller is 10 parts by weight or less, preferably 0.

001-5 parts by weight, more preferably 0.005-3 parts by weight. In this case, if the blending amount of the acid diffusion control agent exceeds 10 parts by weight, the lens of the projection exposure apparatus tends to be contaminated by components eluted from the upper layer film-forming composition.

[0055] The photoresist pattern forming method of the present invention will be described.

In the step of forming a photoresist film by applying a photoresist on the substrate, for example, silicon wafer, a wafer coated with aluminum, or the like can be used as the substrate. Also, in order to maximize the potential of the resist film, an organic or inorganic antireflection film is formed on the substrate to be used, as disclosed in, for example, the Japanese Patent Publication No. 6-12452. Can be formed.

The photoresist to be used can be selected in a timely manner according to the intended use of the resist, which is not particularly limited. Examples of the resist include a chemically amplified positive type or negative type resist containing an acid generator.

In the case of using the upper layer film formed of the composition of the present invention, a positive resist is particularly preferable. In chemically amplified positive resist, the action of acid generated by exposure to acid generator The acid-dissociable organic group in the polymer dissociates to generate, for example, a carboxyl group, and as a result, the solubility of the exposed portion of the resist in the alkali developer is increased, and the exposed portion is dissolved by the alkali developer. This is removed to obtain a positive resist pattern. For the photoresist film, the resin for forming the photoresist film is dissolved in an appropriate solvent, for example, at a solid content concentration of 0.1 to 20% by weight, and then filtered through a filter having a pore diameter of about 30 nm, for example. The resist solution is applied onto the substrate by an appropriate application method such as spin coating, cast coating, roll coating, and pre-baked (hereinafter referred to as “PB”) to volatilize the solvent. To form. In this case, a commercially available resist solution can be used as it is.

[0056] In the step of forming an upper film on the photoresist film using the upper film forming composition, the upper film forming composition of the present invention is applied on the photoresist film, and is usually baked again. Thus, the upper layer film of the present invention is formed. This process forms an upper film for the purpose of protecting the photoresist film and preventing contamination of the lens of the projection exposure apparatus caused by the dissolution of components contained in the resist from the photoresist film into the liquid. It is a process to do. The closer the thickness of the upper layer film is to an odd multiple of λΖ4πι (where λ is the wavelength of radiation and m is the refractive index of the upper layer film), the greater the antireflection effect at the upper interface of the resist film. For this reason, it is preferable that the thickness of the upper layer film be close to this value. In the present invention, any of the pre-baking after the application of the resist solution and the baking after the application of the upper layer film-forming composition solution may be omitted to simplify the process.

[0057] In the process of forming a resist pattern by irradiating the photoresist film and the upper layer film with water through a mask having a predetermined pattern using water as a medium, and then developing it, immersion exposure is performed. This is a step of developing after baking at a temperature of. The water filled between the photoresist film and the upper film can also adjust the pH. In particular, pure water is preferred.

Radiation used for immersion exposure depends on the photoresist film used and the combination of the photoresist film and the upper layer film for immersion, for example, visible light; ultraviolet rays such as g-line and i-line; far-field such as excimer laser Various types of radiation such as ultraviolet rays; X-rays such as synchrotron radiation; and charged particle beams such as electron beams can be selectively used. Especially ArF excimer laser (wavelength 193 nm) Yes !, KrF excimer laser (wavelength 248nm) is preferred! / ヽ.

Further, in order to improve the resolution, pattern shape, developability, etc. of the resist film, it is preferable to perform baking (hereinafter referred to as “PEB”) after exposure. The firing temperature is a force that is appropriately adjusted depending on the resist used, and is usually about 30 to 200 ° C, preferably 50 to 150 ° C.

Next, the photoresist film is developed with a developer and washed to form a desired resist pattern. In this case, the immersion upper film of the present invention is completely removed during the present image or during the cleaning after development, which does not need to be subjected to a separate peeling step. This is one of the important features of the present invention.

Examples of the developer used in forming the resist pattern in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n- Propylamine, jetylamine, di-n-propylamine, triethylamine, methyljetylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1 An alkaline aqueous solution in which 1,5-diazabicyclo [5, 4, 0] -7-undecene, 1,5-diazabicyclo [4, 3, 0] -5-nonane and the like are dissolved can be mentioned. In addition, an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant can be added to these developers. When developing with the above alkaline aqueous solution, it is usually washed with water after development.

Example

[0059] Hereinafter, the present invention will be described more specifically with reference to synthesis examples of copolymers (polymers) and examples of upper layer film compositions. However, the present invention is not limited to these examples. Here, the part is based on mass unless otherwise specified.

[0060] Example of sallow synthesis

Resins (A-1) to (A-10), which can form a stable film in water upon irradiation and dissolve in the developer after forming the resist pattern, were synthesized by the following method. In addition, Mw and Mn of rosin (A-1) to (A-10) are GPC columns (trade names) manufactured by Tosoh Corp. "G2000H"; 2 bottles, "G3000H"; 1 Gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of flow rate 1. OmlZ, elution solvent tetrahydrofuran, column temperature 40 ° C. It was measured by.

The radical polymerizable monomers used for the synthesis of each resin are represented by the following formulas (M-1) to (M-6), (S-1), and (S2).

[Chemical 15]

-1)

C-6)

[0061] Each coconut resin is a single amount obtained by dissolving a monomer and an initiator (2,2′azobis (methyl 2-methylpropionate)) in 200 g of isopropanol in the weights shown in Table 1 in terms of the charged mol%. A body solution was prepared. The total amount of monomers at the time of charging was adjusted to 100 g. The initiator is the number of grams per 100 grams of monomer charge.

To a 1500 ml three-necked flask equipped with a thermometer and a dropping funnel, 100 g of isopropanol was added and purged with nitrogen for 30 minutes. The flask was heated to 80 ° C. while stirring with a magnetic stirrer. The monomer solution prepared earlier was added to the dropping funnel and dropped over 3 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours, and the mixture was cooled to 30 ° C or lower to obtain a copolymer solution.

Each obtained copolymer was post-treated by the method shown below.

[0062] In the post-treatment, the copolymer solution was concentrated to 200 g, and 200 g of methanol and n- The mixture was transferred to a separatory funnel together with 1600 g of heptane, and after stirring sufficiently, the lower layer was separated. The lower layer was mixed with 200 g of methanol and 1600 g of n-heptane, transferred to a separatory funnel, and the lower layer was separated. The lower layer obtained here was solvent-substituted with dibutyl ether. As a comparative example, solvent substitution was performed with 4-methyl-2-pentanol instead of dibutyl ether! /, And each resin was obtained. The solid content concentration of each solvent-substituted sample was calculated from the weight of the residue when heated for 3 hours on a hot plate heated to 140 ° C with 0.3 g of a resin solution placed on an aluminum pan. It was used for subsequent upper layer solution preparation and yield calculation. Mw and MwZMn (dispersion degree of molecular weight) of the resin after solvent substitution with dibutyl ether were measured. The results are also shown in Table 1. The properties of each resin when the solvent was replaced with 4-methyl-2-pentanol were substantially the same.

[0063] [Table 1]

[0064] Preparation of radiation-sensitive rosin composition

A radiation sensitive resin composition for forming a photoresist film was prepared by the following method.

Synthesis of radiation-sensitive rosin (A,)

[Chemical 16]

(1-1) (1-2) (1-3) The above compound (1 1) 53.93 ₈ (50 mol%), compound (1 2) 10. 69 g (10 mole ^_0/0), I匕合objects (1 3) 35. 38 g (40 Monore ^_0/0)溶力2-butanone 195 g, further Jimechinore 2, 2'Azobisu (2-methyl propionate) 2. monomer solution was charged with 24g A 1000 ml three-necked flask charged with 10 Og of 2 butanone was purged with nitrogen for 30 minutes. After the nitrogen purge, the inside of the three-necked flask was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added dropwise using a dropping funnel over 3 hours. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water to 30 ° C. or less, poured into 2000 g of methanol, and the precipitated white powder was separated by filtration.

The filtered white powder was washed twice as a slurry with 400 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powder polymer (72 g, yield 72%). ). This polymer has an Mw of 8,500, and as a result of ¹³ C-NMR analysis, the content of each repeating unit formed is the compound (11), compound (12), compound (1-3) force. 2: 8. 0: 39.8 (mol%) copolymer.

Using this copolymer (Α ′) as a resin component and the other components shown below in the proportions shown in Table 2, a uniform solution was prepared, followed by filtration through a membrane filter having a pore size of 500 nm, and each of the implementations. Each composition solution of the example and the comparative example was prepared. Here, parts are by weight unless otherwise specified.

Acid generator (B)

B-1: Trisulfol sulfone 'nonafluoro-n-butanesulfonate

B— 2: 1— (4— n-Butoxynaphthalene 1-yl) tetrahydrothiophum-nonaf Luoro _n -Butanesulfonate

Acid diffusion controller (C)

C— 1: R— (+) — (tert-Butoxycarbol) 2-piperidinemethanol Solvent (D)

D— 1: γ-Buchiguchi Rataton (GBL)

D-2: Propylene glycol monomethyl ether acetate [PEGMEA] [0066] [Table 2]

[0067] Example 1 to Example 30, Example 37 to Example 48, and Comparative Example 1 to Comparative Example 11

An upper layer film-forming composition for immersion was prepared using the koji resin obtained in the above example. Table 1 The solid content of the resin is 4g and the solvent shown in Table 4 or Table 5 is mixed so that the total weight is 96g. The mixture is stirred for 2 hours and then filtered through a filter with a pore size of 200nm. To prepare a solution. In Table 4, DBE represents dibutyl ether, 4M2P represents 4-methyl-2-pentanol, and DIAE represents diisoamyl ether. In Table 4 or Table 5, the solvent ratio in the case of a mixed solvent represents a weight ratio. The obtained upper layer film-forming composition was evaluated by the following method. The results are shown in Table 4 or Table 5.

[0068] Example 31 to Example 36

Using the resin A-1 obtained in the above example as a resin component, the other components shown below were blended in the proportions shown in Table 3 to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 500 nm. The upper layer film-forming composition for immersion in each example was prepared. Here, the parts are based on weight unless otherwise specified. Evaluation of the obtained upper layer film-forming composition was carried out by the following method. Table 4 shows the results.

Acid or acid generator (Β ')

B'-l: Triphenylsulfo-um 'Nonafluoro-n-butanesulfonate

B, I 3: Perfluorobutanesulfonic acid

Acid diffusion controller (C)

C— 1: R— (+) — (tert-butoxycarbol) 2-piperidinemethanol Solvent (D)

D-3: Dibutyl ether (DBE)

D—4: 4 Methyl 2 pentanol (4M2P)

[Table 3]

Evaluation methods

(1) Method for evaluating solubility (Solubility)

For Example 1 to Example 30, Example 37 to Example 48, and Comparative Example 1 to Comparative Example 10, 4 g of the upper layer membrane resin was added to 96 g of the solvent shown in Table 4 or Table 5, and And stirred at 100 rpm for 3 hours. Each wax used in Example 130 and Example 3748 was obtained by drying the resin solution at 100 ° C. for 24 hours to dryness. After that, if the mixture of rosin and solvent is a uniform solution, it is judged that the solubility is good, “◯”, and if undissolved or white turbidity is seen, the solubility is poor, and “X” did. For Example 31 to Example 36, if the upper layer film-forming composition shown in Table 3 is a homogeneous solution, it is judged that the solubility is good, and “○”, if undissolved or white turbidity is seen The solubility was poor and “X” was assigned.

(2) Evaluation method of upper layer removability (Removability)

Using CLEAN TRACK ACT8 (manufactured by Tokyo Electron Co., Ltd.), the above upper film was spin-coated on an 8-inch silicon wafer and subjected to beta at 90 ° C. for 60 seconds to form a coating film having a thickness of 90 nm. The film thickness was measured using Lambda Ace VM90 (Dainippon Screen Co., Ltd.). This coating was developed with CLEAN TRACK ACT8 for 60 seconds (developer 2. 38% TMAH aqueous solution), spin-dried by shaking, and the wafer surface was observed. At this time, the residue If it was developed vigorously, it was marked as “removable” and “X” if a residue was observed.

[0071] (3) Intermixing evaluation method (intermixing)

Sensitivity using the above-mentioned radiation-sensitive resin (A,) as a resin component on an 8-inch silicon wafer that has been subjected to HMDS treatment (100 ° C, 60 seconds) with CLEAN TRACK ACT8 (manufactured by Tokyo Electron Ltd.) in advance. The radiation resin composition was spin coated, and PB was performed at 130 ° C. for 90 seconds on a hot plate to form a coating film having a predetermined film thickness (300 nm). On this coating film, spin coating of the above upper layer film composition and pre-baking (hereinafter referred to as “PB”) (90 ° C, 60 seconds) to form a coating film with a film thickness of 90 nm, followed by rinsing CLEAN TRACK ACT8 Ultrapure water was discharged from the nozzle onto the wafer for 60 seconds, spin-dried by shaking for 15 seconds at 4000 rpm, and then paddle development was performed for 60 seconds with the LD nozzle using the same CLE AN TRACK ACT8 to remove the upper layer film. In this development step, a 2.38% TMAH aqueous solution was used as a developer. The immersion coating is removed by the development process, but the resist coating is unexposed and remains as it is. Before and after this process, Lambda Ace VM90 (Dainippon Screen Co., Ltd.) was used to measure the film thickness, and if the change in resist film thickness was within 0.5%, the resist film and immersion upper film It was judged that there was no intermixing of “◯”, and when it exceeded 0.5%, it was assigned “X”.

(4) Water stability evaluation of the upper layer film composition for immersion (water resistance)

Lambda Ace is formed on the 8-inch silicon wafer by CLEAN TRACK ACT8 (manufactured by Tokyo Electron Ltd.) and spin-coated by PB (90 ° C, 60 seconds). The film thickness was measured with VM90. Ultra pure water was discharged onto the wafer from the CLEAN TRACK A CT8 rinse nozzle for 60 seconds on the same substrate, and then spin-dried by shaking off at 4000 rpm for 15 seconds. The film thickness of this substrate was measured again. At this time, if the amount of film thickness decrease was within 3% of the initial film thickness, it was judged as stable, and “X” was indicated when it exceeded 3%.

[0072] (5) Patterning evaluation 1

A method for evaluating the patterning of a resist using the upper layer film will be described.

On the 8-inch silicon wafer, CLEAN TRACK ACT8 (manufactured by Tokyo Electron Co., Ltd.) and spin-coating the lower antireflection film ARC29A (manufactured by Brewer Science) by 77 After forming a coating film at nm (PB205 ° C, 60 seconds), patterning of the radiation-sensitive resin composition containing the above-mentioned radiation-sensitive resin (Α) as a resin component was performed. The radiation-sensitive resin composition was applied by spin coating, PB (130 ° C, 90 seconds) to a film thickness of 205 nm, and after PB, the upper layer film was spin-coated, and PB (90 ° C, 60 seconds) was coated. A 90 nm thick coating was formed. Next, with ArF projection exposure system S306C (manufactured by Nikon Corporation), exposure was performed under optical conditions of NA: 0.78, Sigma: 0.85, 2/3 Ann, and more than CLEAN TRACK ACT8 rinse nozzle. Pure water was discharged onto the wafer for 60 seconds, and then spin-dried by shaking off at 4000 rpm for 15 seconds. After that, firing with CLEAN TRACK ACT8 hot plate (hereinafter referred to as “PE BJ” (130 ° C, 90 seconds), paddle development with the LD nozzle of CLEAN TRACK ACT8 (60 seconds), and ultra pure water Rinse and then spin dry at 4000rpm for 15 seconds.

With this scanning electron microscope (S-9380, manufactured by Hitachi Sokki Co., Ltd.), the exposure amount that the line width to be formed in a one-to-one line width in a 90 nm line 'and' space (1L1S) pattern is 90 nm. It was set as the optimal exposure amount. The resolution was determined based on the minimum dimension of the line-and-space pattern after resolving the optimum exposure amount. The results are shown in Table 4. The cross-sectional shape of the 90 nm line 'and' space pattern was observed with a scanning electron microscope (S-4200, manufactured by Hitachi Keiki Co., Ltd.). Figure 1 shows the cross-sectional shape of the line 'and' space pattern. Measure the line width Lb in the middle of the film of pattern 2 formed on the substrate 1 and the line width La in the upper part of the film, 0.9 <= (La-Lb) / Lb <= 1.1 Was evaluated as “rectangular”, (La-Lb) / Lb <0.9 as “tapered”, and ( _La- Lb) / Lb> l.1 as “headlined”.

In the case of Comparative Example 11, the above radiation-sensitive resin composition was spin-coated, applied to a film thickness of 205 nm by PB (130 ° C., 90 seconds), and then the same as above without forming an upper film. The pattern Jung was evaluated.

(6) Patterning evaluation 2

On 8 inch silicon wafer, CLEAN TRACK ACT8 (manufactured by Tokyo Electron Co., Ltd.) and spin-coat the lower antireflection film ARC29A (manufactured by Brewer Science) with a film thickness of 77 nm (PB205 ° C, 60 seconds). After forming, patterning JSR ArF AR1682J Carried out. AR1682J is spin-coated and applied to a film thickness of 205 nm by PB (110 ° C, 90 seconds). After PB, the upper film is spin-coated, and a film with a thickness of 90 nm is applied by PB (90 ° C, 60 seconds). Formed. Next, ArF projection exposure system S306C (Nikon Corp., NA: 0.78, Sigma: 0.85, 2Z3Ann, exposure was performed under the optical conditions of 2Z3Ann, and ultrapure water was applied to the wafer from the CLEAN TRACK ACT8 rinse nozzle. After 60 seconds of discharge, spin dry by shaking for 15 seconds at 4000 rpm, then perform P EB (110 ° C, 90 seconds) on the CLEAN TRACK ACT8 hot plate, and then on the CLEAN TRACK ACT8 LD nozzle. Paddle development (60 seconds), rinse with ultrapure water, then spin dry at 4000 rpm for 15 seconds.

With this scanning electron microscope (S-9380, manufactured by Hitachi Sokki Co., Ltd.), the exposure amount that the line width to be formed in a one-to-one line width in a 90 nm line 'and' space (1L1S) pattern is 90 nm. It was set as the optimal exposure amount. At this optimum exposure amount, the resolution was taken as the minimum dimension of the line-and-space pattern. The results are shown in Table 4. Also, as shown in Fig. 1, the cross-sectional shape of 90nm line 'and' space pattern is observed, and the line width Lb in the middle of the film and the line width La in the upper part of the film are measured, and 0.9 <= ( La-Lb) / Lb <= l. 1 when `` rectangular '', (La-Lb) / Lb <0.9 when `` tapered '', (La-Lb) / Lb> l. 1 Was evaluated as “head tension”.

In Comparative Example 11, AR1682J was applied by spin coating and PB (110 ° C, 90 seconds) to a film thickness of 205 nm, and then pattern ung evaluation was performed in the same manner as described above without forming the upper layer film. .

(7) Minimum application amount

For Example 1 to Example 30, Example 37, and Example 38 to Example 48, the total amount was expressed in weight ratios indicating the solid content of 4 g of the resin shown in Table 1 and the solvent shown in Table 4 or Table 5, respectively. After stirring for 2 hours, the solution was prepared by filtering through a filter with a pore size of 200 nm on an 8-inch silicon wafer using CLE AN TRACK ACT8 (manufactured by Tokyo Electron Ltd.). Application, PB (90 ° C, 60 seconds). The coating amount was changed in increments of 0.25 ml, and the minimum coating amount in which 95% of the surface of the 8-inch silicon wafer was uniformly coated with the above upper layer film composition was measured. For Example 31 to Example 36, the upper layer film-forming composition shown in Table 3 was applied on an 8-inch silicon wafer with CLEAN TRACK ACT8 (manufactured by Tokyo Electron Ltd.), PB (90 ° C., 60 seconds). ,)did. The coating amount was changed in increments of 0.25 ml, and the minimum coating amount in which 95% of the surface of the 8-inch silicon wafer was uniformly coated with the above-mentioned upper layer film yarn and composition was measured.

(8) Suppression ability of elution from resist to ultrapure water (elution of key part)

The center of an 8-inch silicon wafer that had been HMDS treated (100 ° C, 60 seconds) in advance by CLEAN TRACK ACT8 (manufactured by Tokyo Electron Ltd.) was cut into a circle with a center of 30 cm square and a diameter of 11.3 cm in the center. N! / A 1.0 mm thick Taleha Elastomer silicone rubber sheet was placed. Next, 10 ml of ultrapure water was filled in the hollowed out portion of the center of the silicone rubber using a 10 ml hole pipette.

On top of that, spin-coating ARC29A (Brewer Science) underlayer anti-reflection coating on 8 inch silicon wafer using CLEAN TRACK ACT8 (manufactured by Tokyo Electron Co., Ltd.), film thickness 77nm using PB (205 ° C, 60 seconds) After the coating film was formed on the surface, the radiation sensitive resin composition containing the above radiation sensitive resin (Α ') as a resin component was spin coated with CLEAN TRACK ACT8 (manufactured by Tokyo Electron Ltd.), PB ( 115 ° C, 60 seconds), and a film with a thickness of 205 nm is applied. After PB, the upper layer film composition is spin-coated, and PB (90 ° C, 60 seconds) forms a coating with a thickness of 90 nm. It was placed on the surface touched by water, measured with a stopwatch for 10 seconds, and kept in that state. After a lapse of time, the silicon wafer was removed. After the experiment was completed, ultrapure water was collected with a glass syringe and used as a sample for analysis. At this time, the recovery rate of ultrapure water after the experiment was over 95%.

LC-MS (LC part: AGILENT SERIES 1100 MS part: Perseptive Biosys terns, Inc. Mariner) uses a column manufactured by Shiseido Co., Ltd. (trade name “CAPCEL L PAK MG”; one) The flow rate is 0.2 mlZ, water Z is methanol 3Z7, 0.1% by weight of formic acid is added, and the photoacid generation in the ultrapure water obtained by the above experiment under the measurement condition of 35 ° C. The peak intensity at the key-on part of the agent was measured. In that case, the peak intensity of the 1 ppb, 10 ppb, and lOOppb aqueous solution of the photoacid generator used in the radiation-sensitive rosin composition containing the above-mentioned radiation-sensitive rosin (A ′) as a rosin component is A calibration curve was prepared by measuring under the measurement conditions, and the peak strength force elution amount was calculated using this calibration curve. [0076] (9) Viscosity measurement of solvent

The viscosity was measured using a Canon-Fenske viscometer according to the measurement method of JIS K2283.

[0077] [Table 4]

[Table 5]

[0078] As shown in Table 4 and Table 5, Examples 1 to 48 provide an upper layer film composition that forms a stable film in water upon exposure to radiation in immersion exposure and is easily dissolved in an alkaline developer. It is Furthermore, by using a solvent containing ethers or hydrocarbons, the coating amount and elution amount can be reduced while maintaining the same resolution and developability as before, which is extremely advantageous for semiconductor device manufacturing.

Industrial applicability

[0079] The composition for forming an upper film for immersion according to the present invention comprises a resin that forms a stable film in water upon irradiation and dissolves in a developer after forming a resist pattern, and ethers. Or a solvent containing hydrocarbon, so that the lens and photoresist film can be protected during immersion exposure, and a resist pattern with excellent resolution and developability can be formed. It can be used extremely favorably in the production of expected semiconductor devices.

Brief Description of Drawings

[0080] [Fig. 1] A cross-sectional shape of a line and space pattern.

Explanation of symbols

[0081] 1 substrate

2 patterns

Claims

The scope of the claims

[1] An upper film forming composition coated on a photoresist film for forming a pattern by radiation irradiation,

The composition, the photoresist film is dissolved in a developing solution for developing榭脂are dissolve in a solvent, the solvent is a viscosity at 20 ° C is less than 5. 2 X 10- ³ Pa 's An upper layer film-forming composition characterized by the above.

2. The upper layer film-forming composition according to claim 1, wherein the solvent is a solvent that does not cause intermixing between the photoresist film and the upper layer film-forming composition.

[3] The upper layer film-forming composition according to claim 1, wherein the solvent contains a compound represented by the following formula (1).

[Chemical 1]

R ¹ — 0— R ² (1)

(In formula (1), R ¹ and R ² each independently represents a hydrocarbon group having 1 to 8 carbon atoms or a halogenated hydrocarbon group.)

[4] The upper layer film-forming composition according to claim 1, wherein the solvent contains a hydrocarbon compound having 7 to 11 carbon atoms.

[5] The upper layer film-forming composition according to claim 3 or 4, wherein the solvent is a mixed solvent with a monohydric alcohol solvent having 1 to 10 carbon atoms.

[6] The resin has a repeating unit having a group represented by the following formula (2), a repeating unit having a group represented by the following formula (3), and a group represented by the following formula (4). It has at least one repeating unit selected from repeating units, repeating units having a carboxyl group, and repeating units having a sulfo group, and has a weight average molecular weight of 2,000-100 measured by gel permeation chromatography. The composition for forming an upper layer film according to claim 1, wherein

[Chemical 2]

R ⁵

(twenty three)

(In Formula (2), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms. In Formula (3), R ⁵ represents a fluorinated alkyl group having 1 to 20 carbon atoms, and in formula (4), R ⁶ represents an organic group having a polar group.

7. The upper layer film according to claim 6, wherein the composition further comprises at least one component selected from an acid component and an acid generator component that generates acid upon irradiation with radiation CO 2 I-line R _6. Forming composition.

[8] A step of applying a photoresist on a substrate to form a photoresist film, a step of forming an upper layer film on the photoresist film, a liquid as a medium for the photoresist film and the upper layer film, A method of forming a resist pattern by irradiating radiation through a mask having a pattern and then developing the photoresist pattern,

8. The method of forming a photoresist pattern, wherein the step of forming the upper layer film is a step of forming an upper layer film using the upper layer film forming composition according to claim 7.